Nonaqueous electrolytic solution and nonaqueous-electrolyte secondary battery

ABSTRACT

An object of the invention is to provide a nonaqueous electrolytic solution which is capable of bringing about a nonaqueous-electrolyte secondary battery improved in initial charge capacity, input/output characteristics, and impedance characteristics. The invention relates to a nonaqueous electrolytic solution which comprises: a nonaqueous solvent; LiPF 6 ; and a specific fluorosulfonic acid salt, and to a nonaqueous-electrolyte secondary battery containing the nonaqueous electrolytic solution.

The present application is a continuation application of U.S.application Ser. No. 13/572,799 which is a continuation application ofInternational application PCT/JP11/052944 having a filing date of Feb.10, 2011 and claims priority to Japanese patent application 2010-029484having a filing date of Feb. 12, 2010.

TECHNICAL FIELD

The present invention relates to a nonaqueous electrolytic solution anda nonaqueous-electrolyte secondary battery. More particularly, theinvention relates to a nonaqueous electrolytic solution in which LiPF₆and M(FSO₃)_(x) are used in combination in a specific proportion aselectrolytes, and to a nonaqueous-electrolyte secondary battery whichemploys this nonaqueous electrolytic solution.

BACKGROUND ART

Nonaqueous-electrolyte secondary batteries including lithium secondarybatteries are being put to practical use in extensive applicationsranging from power sources for applications for so-called public use,such as portable telephones and notebook type personal computers, tovehicle-mounted power sources for driving motor vehicles or the like andstationary large power sources or the like. However, recentnonaqueous-electrolyte secondary batteries are increasingly required tohave higher performance, and are required to attain batterycharacteristics, such as, for example, high capacity, high output,high-temperature storability, and cycle characteristics, on a highlevel.

Especially in the case where lithium secondary batteries are for use aspower sources for electric vehicles, the lithium secondary batteries arerequired to have high output characteristics and input characteristicsbecause electric vehicles necessitate a large amount of energy whenstarted and accelerated and because the energy which generates in alarge amount upon deceleration must be efficiently regenerated.Furthermore, since electric vehicles are used outdoors, the lithiumsecondary batteries are required to have high input/outputcharacteristics (have low internal impedance) especially at a lowtemperature such as −30° C. in order that the electric vehicles can besmoothly started and accelerated even in the cold season. In addition,the lithium secondary batteries must deteriorate little in capacity andincrease little in internal impedance even when repeatedly charged anddischarged in a high-temperature environment.

Meanwhile, when lithium secondary batteries are used not only inelectric-vehicle applications but also as stationary large powersources, such as various backup applications, applications for levelingthe load of electric power supply, and applications for stabilizing theoutput of electric-power generation by natural energy, then not onlycells having an increased size are used but also a large number of cellsare connected serially or in parallel. Because of this, problemsconcerning reliability and safety due to various kinds ofnon-uniformity, such as unevenness in discharge characteristics amongthe individual cells, unevenness in temperature among the individualcells, and unevenness in capacity or charged state among the individualcells, are apt to arise. In case where a cell assembly such as thatdescribed above is improperly designed or regulated, this poses aproblem, for example, that only some of the cells constituting the cellassembly are kept in a highly charged state or that the internaltemperature of the battery rises, resulting in a high-temperature state.

Namely, the current nonaqueous-electrolyte secondary batteries arerequired to attain the following items on an exceedingly high level: tohave a high initial capacity and high input/output characteristics, tohave a low internal impedance, to have a high capacity retention after adurability test, such as a high-temperature storage test or a cycletest, and to be excellent in terms of input/output performance andimpedance characteristics even after the durability test.

Many techniques have hitherto been investigated with respect to variousbattery components including positive-electrode and negative-electrodeactive materials and nonaqueous electrolytic solutions, as means forimproving the input/output characteristics, impedance characteristics,high-temperature cycle characteristics, and high-temperature storabilityof nonaqueous-electrolyte secondary batteries. For example, patentdocument 1 describes that when LiFSO₃ is used as an electrolyte, abattery which has a high discharge capacity when evaluated for 60° C.charge/discharge cycle characteristics is obtained. Patent document 1includes a statement to the effect that when LiClO₄ is used as anelectrolyte, the LiClO₄ decomposes because of the noble potential of thepositive-electrode active material to generate active oxygen and thisactive oxygen acts on the solvent to accelerate a solvent decompositionreaction. The document further includes a statement to the effect thatwhen CF₃SO₃Li, LiBF₄, and LiPF₆ are used as electrolytes, decompositionof the electrolytes proceeds because of the noble potential of thepositive-electrode active material to generate fluorine and thisfluorine acts on the solvent to accelerate a solvent decompositionreaction.

PRIOR-ART DOCUMENT Patent Document

-   Patent Document 1: JP-A-7-296849

SUMMARY OF THE INVENTION Problems that the Invention is to Solve

According to the disclosure in cited document 1, it is presumed thatwhen LiFSO₃ is used as an electrolyte, a battery having excellentstorability and satisfactory cycle characteristics is obtained becausethe electrolyte itself is chemically and electrochemically stable torender the electrolytic solution less apt to undergo a decompositionreaction.

However, as a result of investigations made by the present inventors, ithas been found that the battery which employs an electrolytic solutioncontaining LiFSO₃ as an electrolyte has a low initial charge capacity, ahigh internal impedance, and low input/output characteristics.

A subject for the invention is to provide a nonaqueous electrolyticsolution which is capable of bringing about a nonaqueous-electrolytesecondary battery that is free from the problems described above and isimproved in initial charge capacity, input/output characteristics, andimpedance characteristics and that therefore not only has initialbattery characteristics and durability but also retains the highinput/output characteristics and the impedance characteristics evenafter a durability test. Another subject is to provide anonaqueous-electrolyte secondary battery which employs the nonaqueouselectrolytic solution.

Means for Solving the Problems

The present inventors diligently made investigations in order toovercome the problems described above. As a result, it has been foundthat a nonaqueous electrolytic solution which is capable of bringingabout a nonaqueous-electrolyte secondary battery improved in initialcharge capacity and input/output characteristics can be renderedpossible by adding LiPF₆ to a nonaqueous electrolytic solution whichcontains at least one fluorosulfonic acid salt represented byM(FSO₃)_(x) and regulating the proportion of the fluorosulfonic acidsalt to the LiPF₆ so as to be in a specific range. The invention hasbeen thus completed.

Namely, the invention relates to the nonaqueous electrolytic solutionand nonaqueous-electrolyte secondary battery described below.

<1>

A nonaqueous electrolytic solution which comprises: a nonaqueoussolvent; LiPF₆; and a fluorosulfonic acid salt represented by formula(1):M(FSO₃)_(x)[wherein

M is a metal atom, N(R)₄, or P(R)₄ (where R is either an organic grouphaving 1-12 carbon atoms or a hydrogen atom (not all of the four R's arehydrogen atoms), the R's may be the same or different, and a part or allof the four R's may form a ring in cooperation with the nitrogen atom orphosphorus atom to which the R's have been bonded);

when M is a metal atom, x indicates the valence of the metal atom M andis an integer of 1 or larger; and when M is N(R)₄ or P(R)₄, x is 1],

wherein the ratio of the molar content of FSO₃ in the nonaqueouselectrolytic solution to the molar content of PF₆ in the nonaqueouselectrolytic solution is 0.001-1.2.

<2>

The nonaqueous electrolytic solution according to the item <1> above,wherein the molar content of FSO₃ in the nonaqueous electrolyticsolution is 0.0005-0.5 mol/L.

<3>

The nonaqueous electrolytic solution according to the item <1> or <2>above, wherein the fluorosulfonic acid salt represented by formula (1)is lithium fluorosulfonate.

<4>

The nonaqueous electrolytic solution according to any one of the items<1> to <3> above, which comprises a cyclic carbonate having a fluorineatom.

<5>

The nonaqueous electrolytic solution according to the item <4> above,which comprises the cyclic carbonate having a fluorine atom in thenonaqueous electrolytic solution in an amount of 0.001-85% by mass.

<6>

The nonaqueous electrolytic solution according to any one of the items<1> to <5> above, which comprises a cyclic carbonate having acarbon-carbon unsaturated bond.

<7>

The nonaqueous electrolytic solution according to the item <6> above,which comprises the cyclic carbonate having a carbon-carbon unsaturatedbond in the nonaqueous electrolytic solution in an amount of 0.001-10%by mass.

<8>

The nonaqueous electrolytic solution according to any one of the items<1> to <7> above, which comprises a cyclic sulfonic acid ester.

<9>

The nonaqueous electrolytic solution according to the item <8> above,which comprises the cyclic sulfonic acid ester in the nonaqueouselectrolytic solution in an amount of 0.001-10% by mass.

<10>

The nonaqueous electrolytic solution according to any one of the items<1> to <9> above, which comprises a compound having a cyano group.

<11>

The nonaqueous electrolytic solution according to the item <10> above,which comprises the compound having a cyano group in the nonaqueouselectrolytic solution in an amount of 0.001-10% by mass.

<12>

The nonaqueous electrolytic solution according to any one of the items<1> to <11> above, which comprises a diisocyanate compound.

<13>

The nonaqueous electrolytic solution according to the item <12> above,which comprises the diisocyanate compound in the nonaqueous electrolyticsolution in an amount of 0.001-5% by mass.

<14>

The nonaqueous electrolytic solution according to any one of the items<1> to <13> above, which comprises at least one salt selected fromfluorophosphoric acid lithium salts other than LiPF₆ and lithium imidesalts.

<15>

The nonaqueous electrolytic solution according to any one of the items<1> to <14> above, which comprises a lithium salt having an oxalic acidgroup.

<16>

The nonaqueous electrolytic solution according to the item <14> above,wherein the concentration of the at least one salt selected fromfluorophosphoric acid lithium salts other than LiPF₆ and lithium imidesalts in the nonaqueous electrolytic solution is 0.0005-0.5 mol/L.

<17>

The nonaqueous electrolytic solution according to the item <15> above,wherein the concentration of the lithium salt having an oxalic acidgroup in the nonaqueous electrolytic solution is 0.0005-0.5 mol/L.

<18>

A nonaqueous-electrolyte secondary battery which comprises: a negativeelectrode and a positive electrode that are capable of occluding andreleasing lithium ions; and the nonaqueous electrolytic solutionaccording to any one of the items <1> to <17> above.

<19>

The nonaqueous-electrolyte secondary battery according to the item <18>above, wherein the negative electrode comprises a current collector anda negative-electrode active-material layer disposed on the currentcollector, the negative-electrode active-material layer containing anegative-electrode active material which comprises at least one memberselected from an elemental metal, alloys and compounds of silicon, andan elemental metal, alloys and compounds of tin.

<20>

The nonaqueous-electrolyte secondary battery according to the item <18>above, wherein the negative electrode comprises a current collector anda negative-electrode active-material layer disposed on the currentcollector, the negative-electrode active-material layer containing anegative-electrode active material which comprises a carbonaceousmaterial.

<21>

The nonaqueous-electrolyte secondary battery according to the item <18>above, wherein the negative electrode comprises a current collector anda negative-electrode active-material layer disposed on the currentcollector, the negative-electrode active-material layer containing anegative-electrode active material which comprises a lithium-titaniumcomposite oxide.

<22>

The nonaqueous-electrolyte secondary battery according to the item <18>above, wherein the positive electrode comprises a current collector anda positive-electrode active-material layer disposed on the currentcollector, the positive-electrode active-material layer containing onemember selected from the group consisting of lithium-cobalt compositeoxides, lithium-manganese composite oxides, lithium-cobalt-manganesecomposite oxides, lithium-nickel composite oxides, lithium-cobalt-nickelcomposite oxides, lithium-nickel-manganese composite oxides, andlithium-nickel-cobalt-manganese composite oxides.

<23>

The nonaqueous-electrolyte secondary battery according to the item <18>above, wherein the positive electrode comprises a current collector anda positive-electrode active-material layer disposed on the currentcollector, the positive-electrode active-material layer containingLi_(x)MPO₄ (M is one element selected from the group consisting of theGroup-4 to Group-11 transition metals belonging to the fourth period ofthe periodic table, and x satisfies 0<x<1.2).

Effects of the Invention

LiPF₆, among the lithium salts used in nonaqueous electrolytic solutionsfor use in lithium secondary batteries, is known to bring about a highelectrical conductivity. For example, when such a nonaqueouselectrolytic solution has been introduced into a battery, the LiPF₆ hasthe effect of reducing the resistance of the electrolytic solutionbetween the positive electrode and the negative electrode. Meanwhile,use of LiFSO₃ as the only electrolyte disadvantageously results in anincrease in the internal impedance of the battery as demonstrated by thepresent inventors.

The inventors have found that by adding a fluorosulfonic acid saltrepresented by M(FSO₃)_(x) as a second electrolyte ingredient to asystem in which LiPF₆ is used as an electrolyte and regulating theseelectrolytes so as to be contained in a specific proportion in thenonaqueous electrolytic solution, the battery is made to have anexcellent feature that the battery has a lower internal impedance andbetter low-temperature output characteristics than the system in whichLiPF₆ is used as the only electrolyte. It is surprising that a batteryemploying a nonaqueous electrolytic solution obtained by adding afluorosulfonic acid salt represented by M(FSO₃)_(x) as a secondelectrolyte ingredient to a system in which LiPF₆ is used as anelectrolyte has a lower internal impedance than the system in whichLiPF₆ is used as the only electrolyte. Thus, batteries employing anonaqueous electrolytic solution which contains two electrolytes, i.e.,LiPF₆ and a fluorosulfonic acid salt represented by M(FSO₃)_(x), incombination show better low-temperature output characteristics andinternal impedance characteristics than batteries in which either ofthese electrolytes is used alone. In addition, the inventors have foundthat the former batteries have improved high-temperature durability andhigh-voltage characteristics and retain the initial internal impedancecharacteristics and high-output characteristics even after a durabilitytest. The invention has been thus completed.

As described above, by using the nonaqueous electrolytic solution of theinvention, a nonaqueous electrolytic solution capable of bringing abouta nonaqueous-electrolyte secondary battery improved in initial chargecapacity, input/output characteristics, and internal impedancecharacteristics is provided. Furthermore, the nonaqueous electrolyticsolution of the invention makes it possible to provide anonaqueous-electrolyte battery which, even after a durability test suchas a high-temperature storage test or a cycle test, has a high capacityretention and excellent input/output performance and further hasexcellent impedance characteristics. Namely, from an industrialstandpoint, it is possible to provide an excellent battery which can beapplied to various fields including the applications shown above such asportable appliances, electric vehicles, and stationary large powersources.

MODES FOR CARRYING OUT THE INVENTION

The invention will be explained below in detail with respect toembodiments thereof. However, the invention should not be construed asbeing limited to the following embodiments, and can be modified at will.

1. Electrolytic Solution

1-1. Electrolytes

<M(FSO₃)_(x)>

In the invention, one or more fluorosulfonic acid salts represented byformula (1): M(FSO₃)_(x) are contained as an electrolyte. [In theformula, M is a metal atom, N(R)₄, or P(R)₄ (where R is either anorganic group having 1-12 carbon atoms or a hydrogen atom (however, notall of the four R's are hydrogen atoms), the R's may be the same ordifferent, and a part or all of the four R's may form a ring incooperation with the nitrogen atom or phosphorus atom to which the R'shave been bonded); when M is a metal atom, x indicates the valence ofthe metal atom M and is an integer of 1 or larger; and when M is N(R)₄or P(R)₄, x is 1.] One such fluorosulfonic acid salt may be used alone,or two or more such fluorosulfonic acid salts may be used incombination.

In formula (1), M represents any of a metal atom, a quaternary ammoniumrepresented by N(R)₄, and a quaternary phosphonium represented by P(R)₄.

When M is a metal atom in formula (1), x indicates the valence of themetal atom and is an integer of 1 or larger. Specific examples thereofinclude 1, 2, or 3. Examples of the metal atom include alkali metalssuch as lithium, sodium, potassium, and cesium, alkaline earth metalssuch as magnesium and calcium, and transition metals such as iron andcopper. It is especially preferred that the metal atom should belithium.

Preferred examples of the fluorosulfonic acid salt include LiFSO₃,NaFSO₃, KFSO₃, CsFSO₃, Mg(FSO₃)₂, Ca(FSO₃)₂, Fe(FSO₃)₂, Cu(FSO₃)₂, andAl(FSO₃)₃. Especially preferred of these are LiFSO₃, NaFSO₃, and KFSO₃.From the standpoint of solubility in the electrolytic solution, LiFSO₃is the most preferred.

When M is a quaternary ammonium represented by N(R)₄ or a quaternaryphosphonium represented by P(R)₄ in formula (1), then x is 1.

In the N(R)₄ or P(R)₄, R is either an organic group having 1-12 carbonatoms or a hydrogen atom (however, not all of the four R's are hydrogenatoms), the R's may be the same or different, and a part or all of thefour R's may form a ring in cooperation with the nitrogen atom orphosphorus atom to which the R's have been bonded.

Examples of the organic group having 1-12 carbon atoms include linear orbranched-chain alkyl groups, cyclic alkyl groups, alkenyl groups,alkynyl groups, aryl groups, and aralkyl groups. These groups may havebeen substituted with halogen atoms. These groups can containheteroatoms, e.g., oxygen, nitrogen, sulfur, phosphorus, and siliconatoms, and the groups may have been bonded to each other through asaturated or unsaturated bond including any of those atoms. Specificexamples include: chain alkyl groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, t-butyl, and sec-butyl; cyclic alkylgroups such as cyclohexyl and norboranyl; alkenyl groups such as vinyl,1-propenyl, allyl, butenyl, and 1,3-butadienyl; alkynyl groups such asethynyl, propynyl, and butynyl; aryl groups such as phenyl which mayhave a substituent, e.g., an alkyl group; aralkyl groups such as benzyland phenylethyl; halogenated alkyl groups such as trifluoromethyl,trifluoroethyl, and hexafluoropropyl; carbonyl-containing alkyl groupssuch as ethoxycarbonylethyl; ether-group-containing alkyl groups such asmethoxyethyl, phenoxymethyl, ethoxyethyl, allyloxyethyl,methoxyethoxyethyl, and ethoxyethoxyethyl; and sulfonyl-containing alkylgroups such as sulfonylmethyl. Examples thereof further includetrialkylsilyl groups such as trimethylsilyl. Preferred are methyl,ethyl, n-propyl, n-butyl, trifluoromethyl, trifluoroethyl, methoxyethyl,methoxyethoxyethyl, and trimethylsilyl.

Preferred examples of the molecular structure of N(R)₄ include:

quaternary ammonium cations represented by tetramethylammonium,tetraethylammonium, and tetrabutylammonium;

pyrrolidinium cations represented by dimethylpyrrolidinium,methylethylpyrrolidinium, and diethylpyrrolidinium;

piperidinium cations represented by dimethylpiperidinium,methylethylpiperidinium, and diethylpiperidinium;

morpholinium cations represented by dimethylmorpholinium,methylethylmorpholinium, and diethylmorpholinium;

pyridinium cations represented by 1-methylpyridinium and1-ethylpyridinium;

pyridazinium cations represented by 1-methylpyridazinium and1-ethylpyridazinium;

pyrimidinium cations represented by 1-methylpyrimidinum and1-ethylpyrimidinium;

pyrazinium cations represented by 1-methylpyrazinium and1-ethylpyrazinium;

imidazolium cations such as 1,3-dimethylimidazolium,1-ethyl-3-methylimidazolium, and 1,2,3-trimethylimidazolium;

oxazolium cations such as 1-methyloxazolium and 1-ethyloxazolium;

thiazolium cations such as 1-methylthiazolium and 1-ethylthiazolium;

pyrazolium cations such as 1-methylpyrazolium and 1-ethylpyrazolium; and

triazolium cations such as 1-methyltriazolium and 1-ethyltriazolium.

Preferred examples of the ammonium cation structures includetetramethylammonium, trimethylethylammonium, trimethylpropylammonium,trimethylbutylammonium, trimethylpentylammonium, trimethylhexylammonium,dimethyldiethylammonium, dimethylethylpropylammonium,dimethylethylbutylammonium, dimethylethylpentylammonium,dimethylethylhexylammonium, dimethyldipropylammonium,dimethylpropylbutylammonium, dimethylpropylpentylammonium,dimethylpropylhexylammonium, dimethyldibutylammonium,dimethylbutylpentylammonium, dimethylbutylhexylammonium,dimethyldipentylammonium, dimethylpentylhexylammonium,dimethyldihexylammonium, methyldiethylpropylammonium,methyldiethylbutylammonium, methyldiethylpentylammonium,methyldiethylhexylammonium, methylethyldipropylammonium,methylethylpropylbutylammonium, methylethylpropylpentylammonium,methylethylpropylhexylammonium, methylethyldibutylammonium,methylethylbutylpentylammonium, methylethylbutylhexylammonium,methylethyldipentylammonium, methylethylpentylhexylammonium,methylethyldihexylammonium, methyltripropylammonium,methyldipropylbutylammonium, methyldipropylpentylammonium,methyldipropylhexylammonium, methylpropyldibutylammonium,methylpropylbutylpentylammonium, methylpropylbutylhexylammonium,methylpropyldipentylammonium, methylpropylpentylhexylammonium,methylpropyldihexylammonium, methyltributylammonium,methyldibutylpentylammonium, methyldibutylhexylammonium,methylbutyldipentylammonium, methylbutylpentylhexylammonium,methylbutyldihexylammonium, methyltripentylammonium,methyldipentylhexylammonium, methylpentyldihexylammonium,methyltrihexylammonium, triethylpropylammonium, triethylbutylammonium,triethylpentylammonium, triethylhexylammonium, and the like or thecations of compounds in which one or more of the hydrogen atoms of thealkyl groups each have been replaced with a fluorine atom. Preferredexamples thereof further include trimethyl allylammonium,trimethylbutenylammonium, trimethylmethoxymethylammonium,trimethylmethoxyethylammonium, and trimethylmethoxyethoxyethyl ammonium.

Preferred examples of the pyrrolidinium cation structures includedimethylpyrrolidinium, methylethylpyrrolidinium, diethylpyrrolidinium,methylpropylpyrrolidinium, ethylpropylpyrrolidinium,dipropylpyrrolidinium, methylbutylpyrrolidinium,ethylbutylpyrrolidinium, propylbutylpyrrolidinium, anddibutylpyrrolidinium or the cations of compounds in which one or more ofthe hydrogen atoms of the alkyl groups each have been replaced with afluorine atom. Preferred examples thereof further includemethylvinylpyrrolidinium, ethylvinylpyrrolidinium,propylvinylpyrrolidinium, butylvinylpyrrolidinium,methylallylpyrrolidinium, ethylallylpyrrolidinium,propylallylpyrrolidinium, butylallylpyrrolidinium, diallylpyrrolidinium,methylbutenylpyrrolidinium, ethylbutenylpyrrolidinium,propylbutenylpyrrolidinium, butylbutenylpyrrolidinium,dibutenylpyrrolidinium, methylmethoxymethylpyrrolidinium,methylmethoxyethylpyrrolidinium, methylethoxyethylpyrrolidinium,methylmethoxyethoxyethylpyrrolidinium,methylethoxyethoxyethylpyrrolidinium, ethylmethoxymethylpyrrolidinium,ethylmethoxyethylpyrrolidinium, ethylethoxyethylpyrrolidinium,ethylmethoxyethoxyethylpyrrolidinium,ethylethoxyethoxyethylpyrrolidinium, propylmethoxymethylpyrrolidinium,propylmethoxyethylpyrrolidinium, propylethoxyethylpyrrolidinium,propylmethoxyethoxyethylpyrrolidinium,propylethoxyethoxyethylpyrrolidinium, butylmethoxymethylpyrrolidinium,butylmethoxyethylpyrrolidinium, butylethoxyethylpyrrolidinium,butylmethoxyethoxyethylpyrrolidinium, and butylethoxyethoxyethylpyrrolidinium.

Preferred examples of the piperidinium cation structures includedimethylpiperidinium, methyl ethylpiperidinium, diethylpiperidinium,methylpropylpiperidinium, ethylpropylpiperidinium, dipropylpiperidinium,methylbutylpiperidinium, ethylbutylpiperidinium,propylbutylpiperidinium, and dibutylpiperidinium or the cations ofcompounds in which one or more of the hydrogen atoms of the alkyl groupseach have been replaced with a fluorine atom. Preferred examples thereoffurther include methylvinylpiperidinium, ethylvinylpiperidinium,propylvinylpiperidinium, butylvinylpiperidinium, methylallylppiperidinium, ethylallylpiperidinium, propylallylpiperidinium,butylallylppiperidinium, diallylpiperidinium, methylbutenylpiperidinium,ethylbutenylpiperidinium, propylbutenylpiperidinium,butylbutenylpiperidinium, dibutenylpiperidinium,methylmethoxymethylpiperidinium, methylmethoxyethylpiperidinium,methylethoxyethylpiperidinium, methylmethoxyethoxyethylpiperidinium,methylethoxyethoxyethylpiperidinium, ethylmethoxymethylpiperidinium,ethylmethoxyethylpiperidinium, ethylethoxyethylpiperidinium,ethylmethoxyethoxyethylpiperidinium, ethylethoxyethoxyethylpiperidinium,propylmethoxymethylpiperidinium, propylmethoxyethylpiperidinium,propylethoxyethylpiperidinium, propylmethoxyethoxyethylpiperidinium,propylethoxyethoxyethylpiperidinium, butylmethoxymethylpiperidinium,butylmethoxyethylpiperidinium, butylethoxyethylpiperidinium,butylmethoxyethoxyethylpiperidinium, andbutylethoxyethoxyethylpiperidinium.

Preferred examples of the morpholinium cation structures includedimethylmorpholinium, methylethylmorpholinium, diethylmorpholinium,methylpropylmorpholinium, ethylpropylmorpholinium, dipropylmorpholinium,methylbutylmorpholinium, ethylbutylmorpholinium,propylbutylmorpholinium, and dibutylmorpholinium or the cations ofcompounds in which one or more of the hydrogen atoms of the alkyl groupseach have been replaced with a fluorine atom. Preferred examples thereoffurther include methylvinylmorpholinium, ethylvinylmorpholinium,propylvinylmorpholinium, butylvinylmorpholinium,methylallylmorpholinium, ethylallylmorpholinium,propylallylmorpholinium, butylallylmorpholinium, diallylmorpholinium,methylbutenylmorpholinium, ethylbutenylmorpholinium,propylbutenylmorpholinium, butylbutenylmorpholinium,dibutenylmorpholinium, methylmethoxymethylmorpholinium,methylmethoxyethylmorpholinium, methylethoxyethylmorpholinium,methylmethoxyethoxyethylmorpholinium,methylethoxyethoxyethylmorpholinium, ethylmethoxymethylmorpholinium,ethylmethoxyethylmorpholinium, ethylethoxyethylmorpholinium,ethylmethoxyethoxyethylmorpholinium, ethylethoxyethoxyethylmorpholinium,propylmethoxymethylmorpholinium, propylmethoxyethylmorpholinium,propylethoxyethylmorpholinium, propylmethoxyethoxyethylmorpholinium,propylethoxyethoxyethylmorpholinium, butylmethoxymethylmorpholinium,butylmethoxyethylmorpholinium, butylethoxyethylmorpholinium,butylmethoxyethoxyethylmorpholinium, andbutylethoxyethoxyethylmorpholinium.

Preferred examples of the pyridinium cation structures include1-ethylpyridinium, 1-propylpyridinium, 1-butylpyridinium,1-pentylpyridinium, 1-hexylpyridinium, 1-allylpyridinium,1-butenylpyridinium, 1-methoxymethylpyridinium, and1-methoxyethylpyridinium.

Preferred examples of the pyridazinium cation structures include1-ethylpyridazinium, 1-propylpyridazinium, 1-butylpyridazinium, 1-pentylpyridazinium, 1-hexylpyridazinium, 1-allylpyridazinium,1-butenylpyridazinium, 1-methoxymethylpyridazinium, and1-methoxyethylpyridazinium.

Preferred examples of the pyrimidinium cation structures include1-ethylpyrimidinium, 1-propylpyrimidinium, 1-butylpyrimidinium,1-pentylpyrimidinium, 1-hexylpyrimidinium, 1-allylpyrimidinium,1-butenylpyrimidinium, 1-methoxymethylpyrimidinium, and1-methoxyethylpyrimidinium.

Preferred examples of the pyrazinium cation structures include1-ethylpyrazinium, 1-propylpyrazinium, 1-butylpyrazinium,1-pentylpyrazinium, 1-hexylpyrazinium, 1-allylpyrazinium,1-butenylpyrazinium, 1-methoxymethylpyrazinium, and1-methoxyethylpyrazinium.

Preferred examples of the imidazolium cation structures include1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium,1-propyl-3-methylimidazolium, 1-butyl-3-methylimidazolium,1-pentyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-propylimidazolium, 1-ethyl-3-butylimidazolium,1-ethyl-3-pentylimidazolium, 1-ethyl-3-hexylimidazolium,1,3-dipropylimidazolium, 1-propyl-3-butylimidazolium,1-propyl-3-pentylimidazolium, 1-hexyl-3-butylimidazolium,1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium,1-propyl-2,3-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium,1-pentyl-2,3-dimethylimidazolium, 1-hexyl-2,3-dimethylimidazolium,1,3-diethyl-2-methylimidazolium, 1-propyl-2-methyl-3-ethylimidazolium,1-butyl-2-methyl-3-ethylimidazolium,1-pentyl-2-methyl-3-ethylimidazolium,1-hexyl-2-methyl-3-ethylimidazolium, 1,2,3,4,5-hexamethylimidazolium,1-ethyl-2,3,4,5-tetramethylimidazolium,1-propyl-2,3,4,5-tetramethylimidazolium,1-butyl-2,3,4,5-tetramethylimidazolium,1-pentyl-2,3,4,5-tetramethylimidazolium, and1-hexyl-2,3,4,5-tetramethylimidazolium or the cations of compounds inwhich one or more of the hydrogen atoms of the alkyl groups each havebeen replaced with a fluorine atom. Preferred examples thereof furtherinclude 1-allyl-3-methylimidazolium, 1-allyl-3-ethylimidazolium,1-allyl-3-propylimidazolium, 1-allyl-3-butylimidazolium,1-allyl-2,3-dimethylimidazolium, 1-allyl-2,3,4,5-tetramethylimidazolium,1-butenyl-3-methylimidazolium, 1-butenyl-3-ethylimidazolium,1-butenyl-3-propylimidazolium, 1-butenyl-3-butylimidazolium,1-butenyl-2,3-dimethylimidazolium,1-butenyl-2,3,4,5-tetramethylimidazolium,1-methoxymethyl-3-methylimidazolium, 1-methoxymethyl-3-ethylimidazolium,1-methoxymethyl-3-propylimidazolium, 1-methoxymethyl-3-butylimidazolium,1-methoxymethyl-2,3-dimethylimidazolium,1-methoxymethyl-2,3,4,5-tetramethylimidazolium,1-methoxyethyl-3-methylimidazolium, 1-methoxyethyl-3-ethylimidazolium,1-methoxyethyl-3-propylimidazolium, 1-methoxyethyl-3-butylimidazolium,1-methoxyethyl-2,3-dimethylimidazolium, and1-methoxyethyl-2,3,4,5-tetramethylimidazolium.

Preferred examples of the oxazolium cation structures include1-ethyloxazolium, 1-propyloxazolium, 1-butyloxazolium,1-pentyloxazolium, 1-hexyloxazolium, 1-allyloxazolium,1-butenyloxazolium, 1-methoxymethyloxazolium, 1-methoxyethyloxazolium,1-ethyl-2,4,5-trimethyloxazolium, 1-propyl-2,4,5-trimethyloxazolium,1-butyl-2,4,5-trimethyloxazolium, 1-pentyl-2,4,5-trimethyloxazolium,1-hexyl-2,4,5-trimethyloxazolium, 1-allyl-2,4,5-trimethyloxazolium,1-butenyl-2,4,5-trimethyloxazolium,1-methoxymethyl-2,4,5-trimethyloxazolium, and1-methoxyethyl-2,4,5-trimethyloxazolium.

Preferred examples of the thiazolium cation structures include1-ethylthiazolium, 1-propylthiazolium, 1-butylthiazolium,1-pentylthiazolium, 1-hexylthiazolium, 1-allylthiazolium,1-butenylthiazolium, 1-methoxymethylthiazolium,1-methoxyethylthiazolium, 1-ethyl-2,4,5-trimethylthiazolium,1-propyl-2,4,5-trimethylthiazolium, 1-butyl-2,4,5-trimethylthiazolium,1-pentyl-2,4,5-trimethylthiazolium, 1-hexyl-2,4,5-trimethylthiazolium,1-allyl-2,4,5-trimethylthiazolium, 1-butenyl-2,4,5-trimethylthiazolium,1-methoxymethyl-2,4,5-trimethylthiazolium, and1-methoxyethyl-2,4,5-trimethylthiazolium.

Preferred examples of the pyrazolium cation structures include1-ethylpyrazolium, 1-propylpyrazolium, 1-butylpyrazol ium,1-pentylpyrazolium, 1-hexylpyrazolium, 1-allylpyrazolium,1-butenylpyrazolium, 1-methoxymethylpyrazolium,1-methoxyethylpyrazolium, 1-ethyl-2,3,4,5-tetramethylpyrazolium,1-propyl-2,3,4,5-tetramethylpyrazolium,1-butyl-2,3,4,5-tetramethylpyrazolium,1-pentyl-2,3,4,5-tetramethylpyrazolium,1-hexyl-2,3,4,5-tetramethylpyrazolium,1-allyl-2,3,4,5-tetramethylpyrazolium,1-butenyl-2,3,4,5-tetramethylpyrazolium,1-methoxymethyl-2,3,4,5-tetramethylpyrazolium, and1-methoxyethyl-2,3,4,5-tetramethylpyrazolium.

Preferred examples of the triazolium cation structures include1-ethyltriazolium, 1-propyltriazolium, 1-butyltriazolium,1-pentyltriazolium, 1-hexyltriazolium, 1-allyltriazolium,1-butenyltriazolium, 1-methoxymethyltriazolium,1-methoxyethyltriazolium, 1-ethyl-2,3,4,5-tetramethyltriazolium,1-propyl-2,3,4,5-tetramethyltriazolium,1-butyl-2,3,4,5-tetramethyltriazolium,1-pentyl-2,3,4,5-tetramethyltriazolium,1-hexyl-2,3,4,5-tetramethyltriazolium,1-allyl-2,3,4,5-tetramethylthiazolium,1-butenyl-2,3,4,5-tetramethyltriazolium,1-methoxymethyl-2,3,4,5-tetramethyltriazolium, and1-methoxyethyl-2,3,4,5-tetramethyltriazolium.

Especially preferred of the fluorosulfonic acid salts which includethose N(R)₄ groups as cation structures, from the standpoints ofavailability and handleability and of giving a battery having a reducedinternal impedance and improved input/output characteristics, aretetramethyl ammonium fluorosulfonate, tetraethylammoniumfluorosulfonate, tetrabutylammonium fluorosulfonate,dimethylpyrrolidinium fluorosulfonate, methylethylpyrrolidiniumfluorosulfonate, diethylpyrrolidinium fluorosulfonate,dimethylpiperidinium fluorosulfonate, methyl ethylpiperidiniumfluorosulfonate, diethylpiperidinium fluorosulfonate,dimethylmorpholinium fluorosulfonate, methylethylmorpholiniumfluorosulfonate, and diethylmorpholinium fluorosulfonate.

Preferred examples of the cation structure P(R)₄ includetriethylbutylphosphonium, triethylpentylphosphonium,triethylhexylphosphonium, triethylheptylphosphonium,triethyloctyiphosphonium, diethylpropylbutylphosphonium,diethylpropylpentylphosphonium, diethylpropylhexylphosphonium,diethylpropylheptylphosphonium, diethylpropyloctylphosphonium,diethylbutylpentylphosphonium, diethylbutylhexylphosphonium,diethylbutylheptylphosphonium, diethylbutyloctylphosphonium,diethylpentylhexylphosphonium, diethylpentylheptylphosphonium,diethylpentyloctylphosphonium, diethylhexylheptylphosphonium,diethylhexyloctylphosphonium, diethylheptyloctylphosphonium,diethyldioctylphosphonium, ethyldipropylbutylphosphonium,ethyldipropylpentylphosphonium, ethyldipropylhexylphosphonium,ethyldipropylheptylphosphonium, ethyldipropyloctylphosphonium,ethylpropyldibutylphosphonium, ethylpropylbutylpentylphosphonium,ethylpropylbutylhexylphosphonium, ethylpropylbutylheptylphosphonium,ethylpropylbutyloctylphosphonium, ethylpropyldipentylphosphonium,ethylpropylpentylhexylphosphonium, ethylpropylpentylheptylphosphonium,ethylpropylpentyloctylphosphonium, ethylpropyldihexylphosphonium,ethylpropylhexylheptylphosphonium, ethylpropylhexyloctylphosphonium,ethylpropyldiheptylphosphonium, ethylpropylheptyloctylphosphonium,ethylpropyldioctylphosphonium, ethyltributylphosphonium,ethyldibutylpentylphosphonium, ethyldibutylhexylphosphonium,ethyldibutylheptylphosphonium, ethyldibutyloctylphosphonium,ethylbutyldipentylphosphonium, ethylbutylpentylhexylphosphonium,ethylbutylpentylheptylphosphonium, ethylbutylpentyloctylphosphonium,ethylbutyldihexylphosphonium, ethylbutylhexylheptylphosphonium,ethylbutylhexyloctylphosphonium, ethylbutylheptyloctylphosphonium,ethylbutyldioctylphosphonium, ethyltripentylphosphonium,ethyldipentylhexylphosphonium, ethyldipentylheptylphosphonium,ethyldipentyloctylphosphonium, ethylpentyldihexylphosphonium,ethylpentylhexylheptylphosphonium, ethylpentylhexyloctylphosphonium,ethylpentyldiheptylphosphonium, ethylpentylheptyloctylphosphonium,ethylpentyldioctylphosphonium, ethyltrihexylphosphonium,ethyldihexylheptylphosphonium, ethyldihexyloctylphosphonium,ethylhexyldiheptylphosphonium, ethylhexylheptyloctylphosphonium,ethylhexyldioctylphosphonium, ethyltriheptylphosphonium,ethyldiheptyloctylphosphonium, ethylheptyldioctylphosphonium,ethyltrioctylphosphonium, tripropylbutylphosphonium,tripropylpentylphosphonium, tripropylhexylphosphonium,tripropylheptylphosphonium, tripropyloctylphosphonium,dipropyldibutylphosphonium, dipropylbutylpentylphosphonium,dipropylbutylhexylphosphonium, dipropylbutylheptylphosphonium,dipropylbutyloctylphosphonium, dipropyldipentylphosphonium,dipropylpentylhexylphosphonium, dipropylpentylheptylphosphonium,dipropylpentyloctylphosphonium, dipropyldihexylphosphonium,dipropylhexylheptylphosphonium, dipropylhexyloctylphosphonium,dipropyldiheptylphosphonium, dipropylheptyloctylphosphonium,dipropyldioctylphosphonium, propyltributylphosphonium,propyldibutylpentylphosphonium, propyldibutylhexylphosphonium,propyldibutylheptylphosphonium, propyldibutyloctylphosphonium,propylbutyldipentylphosphonium, propylbutylpentylhexylphosphonium,propylbutylpentylheptylphosphonium, propylbutylpentyloctylphosphonium,propylbutyldiheptylphosphonium, propylbutylheptyloctylphosphonium,propylbutyldioctylphosphonium, propyltripentylphosphonium,propyldipentylhexylphosphonium, propyldipentylheptylphosphonium,propyldipentyloctylphosphonium, propylpentylhexylheptylphosphonium,propylpentylhexyloctylphosphonium, propylpentyldiheptylphosphonium,propylpentylheptyloctylphosphonium, propylpentyldioctylphosphonium,propyltrihexylphosphonium, propyldihexylheptylphosphonium,propyldihexyloctylphosphonium, propylhexyldiheptylphosphonium,propylhexylheptyloctylphosphonium, propylhexyldioctylphosphonium,propyltriheptylphosphonium, propyldiheptyloctylphosphonium,propylheptyldioctylphosphonium, propyltrioctylphosphonium,tetrabutylphosphonium, tributylpentylphosphonium,tributylhexylphosphonium, tributylheptylphosphonium,tributyloctylphosphonium, tetrapentylphosphonium,tripentylhexylphosphonium, tripentylheptylphosphonium,tripentyloctylphosphonium, tetrahexylphosphonium,trihexylheptylphosphonium, trihexyloctylphosphonium,tetraheptylphosphonium, triheptyloctylphosphonium,tetraoctylphosphonium, and the like or the cations of compounds in whichone or more of the hydrogen atoms of the alkyl groups each have beenreplaced with a fluorine atom. Preferred examples thereof furtherinclude triethylallylphosphonium, triethylbutenylphosphonium,tripropylallylphosphonium, tripropylbutenylphosphonium,tributylallylphosphonium, tributylbutenylphosphonium,triethylmethoxyethylphosphonium, tri ethylmethoxyethoxyethylphosphonium,tripropylmethoxyethylphosphonium,tripropylmethoxyethoxyethylphosphonium, tributylmethoxyethylphosphonium,and tributylmethoxyethoxyethylphosphonium.

Especially preferred of the fluorosulfonic acid salts which includethose P(R)₄ groups as cation structures, from the standpoints ofavailability and handleability, are tetramethylphosphoniumfluorosulfonate, tetraethylphosphonium fluorosulfonate, andtetrabutylphosphonium fluorosulfonate.

Methods for synthesizing and procuring the fluorosulfonic acid saltrepresented by formula (1) to be used in the nonaqueous electrolyticsolution according to the invention are not particularly limited, and asalt represented by formula (1) which has been synthesized using anymethod or which has been procured can be used.

Examples of methods for synthesizing a fluorosulfonic acid metal saltrepresented by formula (1) include: a method in which a metal fluorideor a metal silicofluoride compound is reacted with SO₃ to obtain themetal salt of fluorosulfonic acid; a method in which fluorosulfonic acidis reacted with a metal to obtain the metal salt of fluorosulfonic acidthrough ion exchange; a method in which the ammonium salt offluorosulfonic acid is reacted with a metal to obtain the metal salt offluorosulfonic acid; a method in which fluorosulfonic acid is reactedwith a metal salt of acetic acid to cause the fluorosulfonic acid toundergo ion exchange and thereby obtain the metal salt of fluorosulfonicacid; and a method in which fluorosulfonic acid is reacted with a metalhalide to obtain the metal salt of fluorosulfonic acid. Meanwhile,examples of methods for synthesizing a fluorosulfonic acid ammonium saltor phosphonium salt represented by formula (1) include: a method inwhich a fluorosulfonic acid ester is reacted with a tertiary amine, aphosphine, or the like to obtain the fluorosulfonic acid salt throughthe quaternizing reaction of the tertiary amine or phosphine; and amethod in which a metal salt of fluorosulfonic acid is subjected to ionexchange with a quaternary ammonium or with a halide of a phosphoniumsalt to thereby obtain the ammonium or phosphonium salt offluorosulfonic acid.

The nonaqueous electrolytic solution of the invention contains at leastone fluorosulfonic acid salt represented by formula (1), and thenonaqueous electrolytic solution may contain one such salt alone or maycontain two or more such salts in combination. In the case where two ormore such salts are used, it is preferred that one of these should beLiFSO₃. Especially preferred is a combination of LiFSO₃ and one or moremembers selected from NaFSO₃, KFSO₃, tetraalkylammonium fluorosulfonates(e.g., tetramethylammonium fluorosulfonate, tetraethylammoniumfluorosulfonate, and tetrabutylammonium fluorosulfonate),dimethylpyrrolidinium fluorosulfonate, methylethylpyrrolidiniumfluorosulfonate, diethylpyrrolidinium fluorosulfonate,dimethylpiperidinium fluorosulfonate, methylethylpiperidiniumfluorosulfonate, diethylpiperidinium fluorosulfonate,dimethylmorpholinium fluorosulfonate, methylethylmorpholiniumfluorosulfonate, diethylmorpholinium fluorosulfonate,tetramethylphosphonium fluorosulfonate, tetraethylphosphoniumfluorosulfonate, and tetrabutylphosphonium fluorosulfonate.

Specifically, the following combinations are preferred from thestandpoint of increasing the lithium concentration of the nonaqueouselectrolytic solution: LiFSO₃ and NaFSO₃; LiFSO₃ and KFSO₃; LiFSO₃ andtetramethylammonium fluorosulfonate; LiFSO₃ and tetraethylammoniumfluorosulfonate; LiFSO₃ and tetrabutylammonium fluorosulfonate; LiFSO₃and dimethylpyrrolidinium fluorosulfonate; LiFSO₃ andmethylethylpyrrolidinium fluorosulfonate; LiFSO₃ anddiethylpyrrolidinium fluorosulfonate; LiFSO₃ and dimethylpiperidiniumfluorosulfonate; LiFSO₃ and methylethylpiperidinium fluorosulfonate;LiFSO₃ and diethylpiperidinium fluorosulfonate; LiFSO₃ anddimethylmorpholinium fluorosulfonate; LiFSO₃ and methylethylmorpholiniumfluorosulfonate; LiFSO₃ and diethylmorpholinium fluorosulfonate; LiFSO₃and tetramethylphosphonium fluorosulfonate; LiFSO₃ andtetraethylphosphonium fluorosulfonate; and LiFSO₃ andtetrabutylphosphonium fluorosulfonate.

<LiPF₆>

In the invention, LiPF₆ is contained as an electrolyte.

<Fluorosulfonic Acid Salt Represented by Formula (1) and LiPF₆>

In the invention, the ratio of the molar content of FSO₃[FSO₃] to themolar content of PF₆[PF₆] ([FSO₃]/[PF₆]) in the nonaqueous electrolyticsolution is 0.001-1.2.

When the [FSO₃]/[PF₆] ratio is less than that range, there are caseswhere input/output characteristics and durability, which arecharacteristic of the fluorosulfonic acid salt, are not imparted. On theother hand, when the proportion of the fluorosulfonic acid salt exceedsthat range, there are cases where the resultant battery has an increasedinternal impedance and reduced input/output characteristics. From thestandpoint of more remarkably producing the effects of the invention,the [FSO₃]/[PF₆] is preferably 0.01 or greater, more preferably 0.02 orgreater, and is preferably 1.1 or less, more preferably 1.0 or less,even more preferably 0.7 or less. The range of [FSO₃]/[PF₆] ispreferably 0.01-1.1, more preferably 0.01-1.0, even more preferably0.01-0.7.

In the nonaqueous electrolytic solution of the invention, the molarcontent of FSO₃[FSO₃] in the nonaqueous electrolytic solution is asfollows. The lower limit thereof is preferably 0.0005 mol/L or higher,more preferably 0.01 mol/L or higher, especially preferably 0.02 mol/Lor higher. The upper limit thereof is preferably 0.5 mol/L or less, morepreferably 0.45 mol/L or less, especially preferably 0.4 mol/L or less.When the [FSO₃] concentration is within that range, the resultantbattery has a reduced internal impedance and is more apt to be improvedin input/output characteristics and durability. The range of [FSO₃]concentration is desirably 0.0005-0.5 mol/L, preferably 0.01-0.5 mol/L,more preferably 0.01-0.45 mol/L, especially preferably 0.01-0.40 mol/L.Although the value thereof may be calculated from the addition amount,the value thereof may be determined by analyzing the electrolyticsolution and suitably calculating the value thereof from the amount ofthe electrolyte contained in the electrolytic solution.

Incidentally, the molar content of FSO₃ ([FSO₃]) in a nonaqueouselectrolytic solution can be determined, for example, from the amount ofthe M(FSO₃) which was used when the nonaqueous electrolytic solution wasprepared. In the case where x in formula (1) is 1, the molar content ofthe M(FSO₃) in the nonaqueous electrolytic solution is equal to themolar content [FSO₃]. In the case where x is 2, the molar content [FSO₃]is two times the molar content of the M(FSO₃). When x is 3, the molarcontent [FSO₃] is three times the molar content of the M(FSO₃).

In the nonaqueous electrolytic solution of the invention, the molarcontent of PF₆ ([PF₆]) in the nonaqueous electrolytic solution is asfollows. The lower limit thereof is preferably 0.5 mol/L or higher, morepreferably 0.6 mol/L or higher, especially preferably 0.7 mol/L orhigher. The upper limit thereof is preferably 3.0 mol/L or less, morepreferably 2.0 mol/L or less, especially preferably 1.5 mol/L or less.The range of [PF₆] concentration is preferably 0.5-3.0 mol/L, morepreferably 0.5-2.0 mol/L, even more preferably 0.5-1.5 mol/L.

When the [PF₆] concentration is within that range, the nonaqueouselectrolytic solution has a total ion content which attains anappropriate balance between the amount of ions present and the viscosityof the electrolytic solution. Consequently, this nonaqueous electrolyticsolution is inhibited from having a reduced ionic conductivity, and theresultant battery has a reduced internal impedance and is apt to haveimproved input/output characteristics.

<Other Lithium Salts>

Although LiPF₆ is used as an electrolyte together with an M(FSO₃)_(x),the nonaqueous electrolytic solution according to the invention cancontain one or more other lithium salts. The other lithium salts are notparticularly limited so long as the salts are lithium salts other thanboth LiPF₆ and lithium fluorosulfonate (in the case where M in formula(1) is Li) and are known to be usable in this application. Specificexamples include the following.

Examples thereof include: inorganic lithium salts such as LiBF₄, LiClO₄,LiAlF₄, LiSbF₆, LiTaF₆, and LiWF₇;

fluorophosphoric acid lithium salts other than LiPF₆, such as LiPO₃F andLiPO₂F₂;

tungstic acid lithium salts such as LiWOF₅;

carboxylic acid lithium salts such as HCO₂Li, CH₃CO₂Li, CH₂FCO₂Li,CHF₂CO₂Li, CF₃CO₂Li, CF₃CH₂CO₂Li, CF₃CF₂CO₂Li, CF₃CF₂CF₂CO₂Li, andCF₃CF₂CF₂CF₂CO₂Li;

sulfonic acid lithium salts such as CH₃SO₃Li, CH₂FSO₃Li, CHF₂SO₃Li,CF₃SO₃Li, CF₃CF₂SO₃Li, CF₃CF₂CF₂SO₃Li, and CF₃CF₂CF₂CF₂SO₃Li;

lithium imide salts such as LiN(FCO₂)₂, LiN(FCO)(FSO₂), LiN(FSO₂)₂,LiN(FSO₂)(CF₃SO₂), LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂, the lithium salt ofcyclic 1,2-perfluoroethanedisulfonylimide, the lithium salt of cyclic1,3-perfluoropropanedisulfonylimide, and LiN(CF₃SO₂)(C₄F₉SO₂);

lithium methide salts such as LiC(FSO₂)₃, LiC(CF₃SO₂)₃, andLiC(C₂F₅SO₂)₃;

lithium salt having an oxalic acid groups such as lithiumdifluorooxalatoborate, lithium bis(oxalato)borate, lithiumtetrafluorooxalatophosphate, lithium difluorobis(oxalato)phosphate, andlithium tris(oxalato)phosphate; and

other fluorine-containing organolithium salts such as LiPF₄(CF₃)₂,LiPF₄(C₂F₅)₂, LiPF₄(CF₃SO₂)₂, LiPF₄(C₂F₅SO₂)₂, LiBF₃CF₃, LiBF₃C₂F₅,LiBF₃C₃F₇, LiBF₂(CF₃)₂, LiBF₂(C₂F₅)₂, LiBF₂(CF₃SO₂)₂, andLiBF₂(C₂F₅SO₂)₂.

Preferred of these are LiBF₄, LiSbF₆, LiTaF₆, LiPO₂F₂, CF₃SO₃Li,LiN(FSO₂)₂, LiN(FSO₂)(CF₃SO₂), LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂, the lithiumsalt of cyclic 1,2-perfluoroethanedisulfonylimide, the lithium salt ofcyclic 1,3-perfluoropropanedisulfonylimide, LiC(FSO₂)₃, LiC(CF₃SO₂)₃,LiC(C₂F₅SO₂)₃, lithium bisoxalatoborate, lithium difluorooxalatoborate,lithium tetrafluorooxalatophosphate, lithiumdifluorobisoxalatophosphate, LiBF₃CF₃, LiBF₃C₂F₅, LiPF₃(CF₃)₃,LiPF₃(C₂F₅)₃, and the like.

Furthermore, salts selected from the fluorophosphoric acid lithium saltsother than LiPF₆ and from the lithium imide salts and the lithium saltshaving an oxalic acid group are preferred because these salts have theeffect of improving output characteristics, high-rate charge/dischargecharacteristics, high-temperature storability, cycle characteristics,etc. In particular, the lithium salts are preferred. Specifically,especially preferred are salts selected from LiPO₂F₂, LiBF₄,LiN(CF₃SO₂)₂, LiN(FSO₂)₂, lithium difluorooxalatoborate, lithiumbisoxalatoborate, lithium difluorobisoxalatophosphate, and lithiumtetrafluorobisoxalatophosphate.

The content of such lithium salts other than both M(FSO₃)_(x) and LiPF₆is not limited unless the effects of the invention are significantlylessened thereby. However, the lower limit thereof is preferably 0.0005mol/L or higher, more preferably 0.001 mol/L or higher, especiallypreferably 0.01 mol/L or higher. The upper limit thereof is preferably0.5 mol/L or less, more preferably 0.45 mol/L or less, especiallypreferably 0.4 mol/L or less. When the [FSO₃] concentration is withinthat range, the effect of improving output characteristics, high-ratecharge/discharge characteristics, high-temperature storability, cyclecharacteristics, etc. is more apt to be produced. The range of theconcentration of the lithium salts other than both M(FSO₃)_(x) and LiPF₆in the nonaqueous electrolytic solution is preferably 0.0005-0.5 mol/L,more preferably 0.001-0.45 mol/L, especially preferably 0.001-0.4 mol/L.

It is preferred that an M(FSO₃)_(x), LiPF₆, and other lithium salt(s)should be used so that the nonaqueous electrolytic solution has a totalmolar concentration of lithium [Li] of 0.3-3 mol/L, from the standpointsof making the electrolytic solution have an electrical conductivitywithin a satisfactory range and thereby ensuring satisfactory batteryperformances. The total molar concentration of lithium [Li] includes theconcentration of the lithium derived from the LiPF₆ and, in the casewhere the fluorosulfonic acid salt represented by formula (1) is alithium salt, from this fluorosulfonic acid salt, and that term meansthe total molar concentration of lithium [Li] in the nonaqueouselectrolytic solution. The total molar concentration of lithium [Li] ismore preferably 0.4 mol/L or higher, even more preferably 0.5 mol/L orhigher, and is more preferably 2.0 mol/L or less, even more preferably1.8 mol/L or less, especially preferably 1.7 mol/L or less.

In the case where an electrolytic solution which contains LiPO₂F₂ is tobe prepared, examples of methods for preparing this electrolyticsolution include: a method in which LiPO₂F₂ that has been separatelysynthesized by a known technique is added to an electrolytic solutioncontaining LiPF₆; and a method in which water is caused to coexist withbattery components which will be described later, e.g., active materialsand electrode plates, and LiPO₂F₂ is generated in the system when abattery is assembled using an electrolytic solution which containsLiPF₆. Either of these techniques may be used in the invention.

Techniques for determining the amount of LiPO₂F₂ contained in thenonaqueous electrolytic solution and in a nonaqueous-electrolyte batteryare not particularly limited, and known techniques can be used at will.Examples thereof include ion chromatography and F nuclear magneticresonance spectroscopy (hereinafter sometimes abbreviated to NMR).

1-2. Nonaqueous Solvent

<Saturated Cyclic Carbonates>

Examples of saturated cyclic carbonates include saturated cycliccarbonates which have an alkylene group having 2-4 carbon atoms.

Specifically, examples of the saturated cyclic carbonates having 2-4carbon atoms include ethylene carbonate, propylene carbonate, andbutylene carbonate. Of these, ethylene carbonate and propylene carbonateare especially preferred from the standpoint of an improvement inbattery characteristics which is due to an improvement in the degree ofdissociation into lithium ions.

One of such saturated cyclic carbonates may be used alone, or anydesired two or more thereof may be used in combination in any desiredproportion.

The amount of the saturated cyclic carbonate(s) to be incorporated isnot particularly limited unless the effects of the invention areconsiderably lessened thereby. However, in the case where one saturatedcyclic carbonate is used alone, the lower limit of the incorporationamount thereof is 3% by volume or more, more preferably 5% by volume ormore, per 100% by volume the nonaqueous solvent. By regulating theamount thereof so as to be within that range, a decrease in electricalconductivity due to a decrease in the permittivity of the nonaqueouselectrolytic solution is avoided to make it easy to regulate thehigh-current discharge characteristics of the nonaqueous-electrolytesecondary battery, stability to the negative electrode, and cyclecharacteristics so as to be within satisfactory ranges. The upper limitthereof is 90% by volume or less, more preferably 85% by volume or less,even more preferably 80% by volume or less. By regulating the amountthereof so as to be within that range, the nonaqueous electrolyticsolution is made to have a viscosity within an adequate range and isinhibited from decreasing in ionic conductivity. This in turn makes iteasy to regulate the load characteristics of the nonaqueous-electrolytesecondary battery so as to be within a satisfactory range.

Meanwhile, any desired two or more saturated cyclic carbonates can beused in combination. One of preferred combinations is a combination ofethylene carbonate and propylene carbonate. The volume ratio of ethylenecarbonate to propylene carbonate in this case is preferably from 99:1 to40:60, especially preferably from 95:5 to 50:50. Furthermore, theproportion of the propylene carbonate in the whole nonaqueous solvent is1% by volume or more, preferably 2% by volume or more, more preferably3% by volume or more, and the upper limit thereof is generally 20% byvolume or less, preferably 8% by volume or less, more preferably 5% byvolume or less. The nonaqueous electrolytic solution which containspropylene carbonate in an amount within that range is preferred becausethis electrolytic solution has excellent low-temperature propertieswhile retaining the properties due to a combination of ethylenecarbonate and a dialkyl carbonate.

<Chain Carbonates>

Preferred chain carbonates are chain carbonates having 3-7 carbon atoms.

Specifically, examples of the chain carbonates having 3-7 carbon atomsinclude dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate,diisopropyl carbonate, n-propyl isopropyl carbonate, ethyl methylcarbonate, methyl n-propyl carbonate, n-butyl methyl carbonate, isobutylmethyl carbonate, t-butyl methyl carbonate, ethyl n-propyl carbonate,n-butyl ethyl carbonate, isobutyl ethyl carbonate, and t-butyl ethylcarbonate.

Preferred of these are dimethyl carbonate, diethyl carbonate,di-n-propyl carbonate, diisopropyl carbonate, n-propyl isopropylcarbonate, ethyl methyl carbonate, and methyl n-propyl carbonate.Especially preferred are dimethyl carbonate, diethyl carbonate, andethyl methyl carbonate.

Chain carbonates having one or more fluorine atoms (hereinafter oftenreferred to simply as “fluorinated chain carbonates”) also are suitablefor use. The number of the fluorine atoms possessed by each of thefluorinated chain carbonates is not particularly limited so long as thenumber thereof is 1 or larger. However, the number thereof is generally6 or less, preferably 4 or less. In the case where a fluorinated chaincarbonate has a plurality of fluorine atoms, these fluorine atoms mayhave been bonded to the same carbon atom or may have been bonded todifferent carbon atoms. Examples of the fluorinated chain carbonatesinclude fluorinated dimethyl carbonate derivatives, fluorinated ethylmethyl carbonate derivatives, and fluorinated diethyl carbonatederivatives.

Examples of the fluorinated dimethyl carbonate derivatives includefluoromethyl methyl carbonate, difluoromethyl methyl carbonate,trifluoromethyl methyl carbonate, bis(fluoromethyl) carbonate,bis(difluoro)methyl carbonate, and bis(trifluoromethyl) carbonate.

Examples of the fluorinated ethyl methyl carbonate derivatives include2-fluoroethyl methyl carbonate, ethyl fluoromethyl carbonate,2,2-difluoroethyl methyl carbonate, 2-fluoroethyl fluoromethylcarbonate, ethyl difluoromethyl carbonate, 2,2,2-trifluoroethyl methylcarbonate, 2,2-difluoroethyl fluoromethyl carbonate, 2-fluoroethyldifluoromethyl carbonate, and ethyl trifluoromethyl carbonate.

Examples of the fluorinated diethyl carbonate derivatives include ethyl2-fluoroethyl carbonate, ethyl 2,2-difluoroethyl carbonate,bis(2-fluoroethyl) carbonate, ethyl (2,2,2-trifluoro ethyl) carbonate,2,2-difluoroethyl 2′-fluoro ethyl carbonate, bis(2,2-difluoroethyl)carbonate, 2,2,2-trifluoroethyl 2′-fluoroethyl carbonate,2,2,2-trifluoroethyl 2′,2′-difluoroethyl carbonate, andbis(2,2,2-trifluoroethyl) carbonate.

One of such chain carbonates may be used alone, or any desired two ormore thereof may be used in combination in any desired proportion.

It is preferred that one or more chain carbonates should be contained inan amount of 15% by volume or more per 100% by volume the nonaqueoussolvent. By regulating the amount thereof to 15% by volume or more, thenonaqueous electrolytic solution is made to have a viscosity within anadequate range and is inhibited from decreasing in ionic conductivity.This in turn makes it easy to regulate the high-current dischargecharacteristics of the nonaqueous-electrolyte secondary battery so as tobe within a satisfactory range. Furthermore, it is preferred that theamount of the chain carbonate(s) should be 90% by volume or less per100% by volume the nonaqueous solvent. By regulating the amount thereofto 90% by volume or less, a decrease in electrical conductivity due to adecrease in the permittivity of the nonaqueous electrolytic solution isavoided to make it easy to regulate the high-current dischargecharacteristics of the nonaqueous-electrolyte secondary battery so as tobe within a satisfactory range. The amount of the chain carbonate(s) tobe incorporated is more preferably 20% by volume or more, even morepreferably 25% by volume or more, and is more preferably 85% by volumeor less, even more preferably 80% by volume or less.

Furthermore, by using one or more specific chain carbonates incombination with ethylene carbonate in specific incorporation amounts,battery performances can be remarkably improved.

For example, in the case where dimethyl carbonate and ethyl methylcarbonate were selected as the specific chain carbonates, it ispreferred that ethylene carbonate should be incorporated in an amount of15-40% by volume, dimethyl carbonate be incorporated in an amount of20-50% by volume, and ethyl methyl carbonate be incorporated in anamount of 20-50% by volume. By selecting such incorporation amounts, theviscosity of the nonaqueous electrolytic solution can be reduced, whilelowering the lower-temperature-side precipitation temperature of theelectrolytes, to improve ionic conductivity and thereby enable thenonaqueous-electrolyte secondary battery to produce high output even atlow temperatures. It is especially preferred that the amount of ethylenecarbonate to be incorporated should be 25-35% by volume, that ofdimethyl carbonate to be incorporated should be 30-40% by volume, andthat of ethyl methyl carbonate to be incorporated should be 30-40% byvolume.

<Cyclic Carbonates Having Fluorine Atom(s)>

Cyclic carbonates having one or more fluorine atoms (hereinafter oftenreferred to simply as “fluorinated cyclic carbonates”) are notparticularly limited so long as the carbonates are cyclic carbonateshaving one or more fluorine atoms.

Examples of the fluorinated cyclic carbonates include derivatives ofcyclic carbonates which have an alkylene group having 2-6 carbon atoms,e.g., derivatives of ethylene carbonate. Examples of the ethylenecarbonate derivatives include products of fluorination of eitherethylene carbonate or ethylene carbonate substituted with one or morealkyl groups (e.g., alkyl groups having 1-4 carbon atoms). Preferred ofthese are such fluorinated carbonates having 1-8 fluorine atoms.

Specific examples thereof include monofluoroethylene carbonate,4,4-difluoroethylene carbonate, 4,5-di fluoroethylene carbonate,4-fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methyl ethyl enecarbonate, 4-fluoro-5-methyl ethyl en e carbonate,4,4-difluoro-5-methylethylene carbonate, 4-(fluoromethyl)ethylenecarbonate, 4-(difluoromethyl)ethylene carbonate,4-(trifluoromethyl)ethylene carbonate, 4-(fluoromethyl)-4-fluoroethylenecarbonate, 4-(fluoromethyl)-5-fluoroethylene carbonate,4-fluoro-4,5-dimethylethylene carbonate,4,5-difluoro-4,5-dimethylethylene carbonate, and4,4-difluoro-5,5-dimethylethylene carbonate.

More preferred of these, from the standpoints of imparting high ionicconductivity and suitably forming an interface-protective coating film,is at least one member selected from the group consisting ofmonofluoroethylene carbonate, 4,4-difluoroethylene carbonate,4,5-difluoroethyl ene carbonate, and 4,5-difluoro-4,5-dimethylethylenecarbonate.

One of such fluorinated cyclic carbonates may be used alone, or anydesired two or more thereof may be used in combination in any desiredproportion. The amount of the fluorinated cyclic carbonate(s) to beincorporated is not particularly limited unless the effects of theinvention are considerably lessened thereby. However, the amount thereofper 100% by mass the nonaqueous electrolytic solution is preferably0.001% by mass or more, more preferably 0.01% by mass or more, even morepreferably 0.1% by mass or more, and is preferably 85% by mass or less,more preferably 80% by mass or less, even more preferably 75% by mass orless. The range of the concentration of the fluorinated cycliccarbonate(s) is preferably 0.001-85% by mass, more preferably 0.01-80%by mass, even more preferably 0.1-75% by mass.

Incidentally, a fluorinated cyclic carbonate may be used either as amain solvent for the nonaqueous electrolytic solution or as a minorsolvent therefor. In the case where a fluorinated cyclic carbonate isused as a main solvent, the amount of this carbonate to be incorporatedper 100% by mass the nonaqueous electrolytic solution is preferably 8%by mass or more, more preferably 10% by mass or more, even morepreferably 12% by mass or more, and is preferably 85% by mass or less,more preferably 80% by mass or less, even more preferably 75% by mass orless. So long as the amount thereof is within that range, the effect ofsufficiently improving the cycle characteristics of thenonaqueous-electrolyte secondary battery is apt to be produced and it iseasy to prevent the battery from decreasing in discharge capacityretention. In the case where a fluorinated cyclic carbonate is used as aminor solvent, the amount of this carbonate to be incorporated per 100%by mass the nonaqueous electrolytic solution is preferably 0.001% bymass or more, more preferably 0.01% by mass or more, even morepreferably 0.1% by mass or more, and is preferably 8% by mass or less,more preferably 6% by mass or less, even more preferably 5% by mass orless. So long as the amount thereof is within that range, thenonaqueous-electrolyte secondary battery is apt to have sufficientoutput characteristics.

<Chain Carboxylic Acid Esters>

Examples of chain carboxylic acid esters include chain carboxylic acidesters represented by a structural formula in which the total number ofcarbon atoms is 3-7.

Specific examples thereof include methyl acetate, ethyl acetate,n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate,t-butyl acetate, methyl propionate, ethyl propionate, n-propylpropionate, isopropyl propionate, n-butyl propionate, isobutylpropionate, t-butyl propionate, methyl butyrate, ethyl butyrate,n-propyl butyrate, isopropyl butyrate, methyl isobutyrate, ethylisobutyrate, n-propyl isobutyrate, and isopropyl isobutyrate.

Preferred of these, from the standpoint of an improvement in ionicconductivity due to a decrease in viscosity, are methyl acetate, ethylacetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethylpropionate, n-propyl propionate, isopropyl propionate, methyl butyrate,ethyl butyrate, and the like.

It is preferred that the amount of such a chain carboxylic acid estershould be 5% by volume or more per 100% by volume the nonaqueoussolvent. By regulating the amount thereof to 5% by volume or more, theelectrical conductivity of the nonaqueous electrolytic solution isimproved to make it easy to improve the high-current dischargecharacteristics of the nonaqueous-electrolyte secondary battery. It isalso preferred that the amount of the chain carboxylic acid ester shouldbe 80% by volume or less per 100% by volume the nonaqueous solvent. Byregulating the amount thereof to 80% by volume or less,negative-electrode resistance is inhibited from increasing and thenonaqueous-electrolyte secondary battery is made to be easily regulatedso as to have satisfactory high-current discharge characteristics andsatisfactory cycle characteristics. The amount of the chain carboxylicacid ester to be incorporated is more preferably 8% by volume or more,and is more preferably 70% by volume or less.

<Cyclic Carboxylic Acid Esters>

Examples of cyclic carboxylic acid esters include cyclic carboxylic acidesters represented by a structural formula in which the total number ofcarbon atoms is 3-12.

Specific examples thereof include γ-butyrolactone, γ-valerolactone,γ-caprolactone, and ε-caprolactone. Especially preferred of these isγ-butyrolactone from the standpoint of an improvement in batterycharacteristics due to an improvement in the degree of dissociation intolithium ions.

It is preferred that the amount of such a cyclic carboxylic acid estershould be 3% by volume or more per 100% by volume the nonaqueoussolvent. By regulating the amount thereof to 3% by volume or more, theelectrical conductivity of the nonaqueous electrolytic solution isimproved to make it easy to improve the high-current dischargecharacteristics of the nonaqueous-electrolyte secondary battery. It isalso preferred that the amount of the cyclic carboxylic acid estershould be 60% by volume or less. By regulating the amount thereof to 60%by volume or less, the nonaqueous electrolytic solution is made to havea viscosity within an appropriate range and is prevented from decreasingin electrical conductivity and negative-electrode resistance isinhibited from increasing. This makes it easy to regulate thehigh-current discharge characteristics of the nonaqueous-electrolytesecondary battery so as to be within a satisfactory range. The amount ofthe cyclic carboxylic acid ester to be incorporated is more preferably5% by volume or more, and is more preferably 50% by volume or less.

<Ether Compounds>

Preferred ether compounds are chain ethers having 3-10 carbon atoms andcyclic ethers having 3-6 carbon atoms.

Examples of the chain ethers having 3-10 carbon atoms include diethylether, di(2-fluoroethyl)ether, di(2,2-difluoroethyl)ether,di(2,2,2-trifluoroethyl)ether, ethyl (2-fluoroethyl)ether, ethyl2,2,2-trifluoroethyl ether, ethyl (1,1,2,2-tetrafluoroethyl) ether,(2-fluoroethyl) (2,2,2-trifluoro ethyl)ether, (2-fluoroethyl)(1,1,2,2-tetrafluoroethyl)ether, (2,2,2-trifluoroethyl)(1,1,2,2-tetrafluoroethyl)ether, ethyl n-propyl ether, ethyl(3-fluoro-n-propyl)ether, ethyl (3,3,3-trifluoro-n-propyl) ether, ethyl(2,2,3,3-tetrafluoro-n-propyl)ether, ethyl(2,2,3,3,3-pentafluoro-n-propyl) ether, 2-fluoro ethyl n-propyl ether,(2-fluoro ethyl) (3-fluoro-n-propyl)ether, (2-fluoroethyl)(3,3,3-trifluoro-n-propyl)ether, (2-fluoroethyl)(2,2,3,3-tetrafluoro-n-propyl)ether, (2-fluoroethyl)(2,2,3,3,3-pentafluoro-n-propyl) ether, 2,2,2-trifluoroethyl n-propylether, (2,2,2-trifluoroethyl) (3-fluoro-n-propyl)ether,(2,2,2-trifluoroethyl) (3,3,3-trifluoro-n-propyl)ether,(2,2,2-trifluoroethyl) (2,2,3,3-tetrafluoro-n-propyl)ether,(2,2,2-trifluoroethyl) (2,2,3,3,3-pentafluoro-n-propyl)ether,1,1,2,2-tetrafluoroethyl n-propyl ether, (1,1,2,2-tetrafluoroethyl)(3-fluoro-n-propyl)ether, (1,1,2,2-tetrafluoroethyl)(3,3,3-trifluoro-n-propyl)ether, (1,1,2,2-tetrafluoroethyl)(2,2,3,3-tetrafluoro-n-propyl) ether, (1,1,2,2-tetrafluoroethyl)(2,2,3,3,3-pentafluoro-n-propyl)ether, di-n-propyl ether, (n-propyl)(3-fluoro-n-propyl)ether, (n-propyl) (3,3,3-trifluoro-n-propyl)ether,(n-propyl) (2,2,3,3-tetrafluoro-n-propyl)ether, (n-propyl)(2,2,3,3,3-pentafluoro-n-propyl)ether, di(3-fluoro-n-propyl)ether,(3-fluoro-n-propyl) (3,3,3-tri fluoro-n-propyl)ether,(3-fluoro-n-propyl) (2,2,3,3-tetrafluoro-n-propyl)ether,(3-fluoro-n-propyl) (2,2,3,3,3-pentafluoro-n-propyl)ether,di(3,3,3-trifluoro-n-propyl) ether, (3,3,3-trifluoro-n-propyl)(2,2,3,3-tetrafluoro-n-propyl)ether, (3,3,3-trifluoro-n-propyl)(2,2,3,3,3-pentafluoro-n-propyl)ether,di(2,2,3,3-tetrafluoro-n-propyl)ether, (2,2,3,3-tetrafluoro-n-propyl)(2,2,3,3,3-pentafluoro-n-propyl)ether,di(2,2,3,3,3-pentafluoro-n-propyl)ether, di-n-butyl ether,dimethoxymethane, methoxyethoxymethane, methoxy(2-fluoroethoxy)methane,methoxy(2,2,2-trifluoroethoxy)methanemethoxy(1,1,2,2-tetrafluoroethoxy)methane, diethoxymethane,ethoxy(2-fluoroethoxy)methane, ethoxy(2,2,2-trifluoroethoxy)methane,ethoxy(1,1,2,2-tetrafluoroethoxy)methane, di(2-fluoroethoxy)methane,(2-fluoroethoxy)(2,2,2-trifluoroethoxy)methane,(2-fluoroethoxy)(1,1,2,2-tetrafluoroethoxy)methanedi(2,2,2-trifluoroethoxy)methane,(2,2,2-trifluoroethoxy)(1,1,2,2-tetrafluoroethoxy)methane,di(1,1,2,2-tetrafluoroethoxy)methane, dimethoxyethane,methoxyethoxyethane, methoxy(2-fluoroethoxy)ethane,methoxy(2,2,2-trifluoroethoxy)ethane,methoxy(1,1,2,2-tetrafluoroethoxy)ethane, di ethoxyethane,ethoxy(2-fluoroethoxy)ethane, ethoxy(2,2,2-trifluoroethoxy)ethane,ethoxy(1,1,2,2-tetrafluoroethoxy)ethane, di(2-fluoroethoxy)ethane,(2-fluoroethoxy)(2,2,2-tri fluoroethoxy)ethane,(2-fluoroethoxy)(1,1,2,2-tetrafluoroethoxy)ethane,di(2,2,2-trifluoroethoxy)ethane,(2,2,2-trifluoroethoxy)(1,1,2,2-tetrafluoroethoxy)ethane,di(1,1,2,2-tetrafluoroethoxy)ethane, ethylene glycol di-n-propyl ether,ethylene glycol di-n-butyl ether, and diethylene glycol dimethyl ether.

Examples of the cyclic ethers having 3-6 carbon atoms includetetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran,1,3-dioxane, 2-methyl-1,3-dioxane, 1,4-methyl-1,3-dioxane, 1,4-dioxane,and the like and compounds formed by fluorinating these compounds.

Preferred of these are dimethoxymethane, diethoxymethane,ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycoldi-n-butyl ether, and diethylene glycol dimethyl ether, from thestandpoint that these compounds have the high ability to solvate lithiumions and improve the property of dissociating into ions. Especiallypreferred are dimethoxymethane, diethoxymethane, andethoxymethoxymethane, because these compounds have a low viscosity andimpart a high ionic conductivity.

The amount of such an ether compound to be incorporated per 100% byvolume the nonaqueous solvent usually is preferably 3% by volume ormore, more preferably 4% by volume or more, even more preferably 5% byvolume or more, and is preferably 70% by volume or less, more preferably65% by volume or less, even more preferably 60% by volume or less. Solong as a chain ether is incorporated in an amount within this range, itis easy to ensure the effects of the chain ether, i.e., an improvementin the degree of dissociation into lithium ions and an improvement inionic conductivity due to a decrease in viscosity. In addition, in thecase where the negative-electrode active material is a carbonaceousmaterial, it is easy to avoid the trouble that the chain ether isinserted together with lithium ions to cause a decrease in capacity.

<Sulfone Compounds>

Preferred sulfone compounds are cyclic sulfones having 3-6 carbon atomsand chain sulfones having 2-6 carbon atoms. It is preferred that thenumber of sulfonyl groups per molecule should be 1 or 2.

Examples of the cyclic sulfones include monosulfone compounds such astrimethylene sulfone compounds, tetramethylene sulfone compounds, andhexamethylene sulfone compounds and disulfone compounds such astrimethylene disulfone compounds, tetramethylene disulfone compounds,and hexamethylene disulfone compounds. From the standpoints ofpermittivity and viscosity, tetramethylene sulfone compounds,tetramethylene disulfone compounds, hexamethylene sulfone compounds, andhexamethylene disulfone compounds are more preferred of those, andtetramethylene sulfone compounds (sulfolane compounds) are especiallypreferred.

The sulfolane compounds preferably are sulfolane and/or sulfolanederivatives (hereinafter, these compounds including sulfolane are oftenreferred to simply as “sulfolane compounds”). The sulfolane derivativespreferably are sulfolane compounds in which one or more of the hydrogenatoms bonded to the carbon atoms constituting the sulfolane ring eachhave been replaced with a fluorine atom or an alkyl group.

Preferred of these are 2-methylsulfolane, 3-methylsulfolane,2-fluorosulfolane, 3-fluorosulfolane, 2,2-difluorosulfolane,2,3-difluorosulfolane, 2,4-difluorosulfolane, 2,5-difluoro sulfo lane,3,4-difluoro sulfolane, 2-fluoro-3-methylsulfolane,2-fluoro-2-methylsulfolane, 3-fluoro-3-methylsulfolane,3-fluoro-2-methyl sulfolane, 4-fluoro-3-methylsulfolane,4-fluoro-2-methylsulfolane, 5-fluoro-3-methylsulfolane,5-fluoro-2-methylsulfolane, 2-fluoromethylsulfolane,3-fluoromethylsulfolane, 2-difluoromethylsulfolane,3-difluoromethylsulfolane, 2-trifluoromethyl sulfolane,3-trifluoromethyl sulfolan e, 2-fluoro-3-(trifluoromethyl)sulfolane,3-fluoro-3-(trifluoromethyl)sulfolane,4-fluoro-3-(trifluoromethyl)sulfolane,5-fluoro-3-(trifluoromethyl)sulfolane, and the like, from the standpointthat these sulfolane compounds have a high ionic conductivity and bringabout high input/output characteristics.

Examples of the chain sulfones include dimethyl sulfone, ethyl methylsulfone, diethyl sulfone, n-propyl methyl sulfone, n-propyl ethylsulfone, di-n-propyl sulfone, isopropyl methyl sulfone, isopropyl ethylsulfone, diisopropyl sulfone, n-butyl methyl sulfone, n-butyl ethylsulfone, t-butyl methyl sulfone, t-butyl ethyl sulfone, monofluoromethylmethyl sulfone, difluoromethyl methyl sulfone, trifluoromethyl methylsulfone, monofluoroethyl methyl sulfone, difluoroethyl methyl sulfone,trifluoroethyl methyl sulfone, pentafluoroethyl methyl sulfone, ethylmonofluoromethyl sulfone, ethyl difluoromethyl sulfone, ethyltrifluoromethyl sulfone, perfluoroethyl methyl sulfone, ethyltrifluoroethyl sulfone, ethyl pentafluoroethyl sulfone,di(trifluoroethyl) sulfone, perfluorodiethyl sulfone, fluoromethyln-propyl sulfone, difluoromethyl n-propyl sulfone, trifluoromethyln-propyl sulfone, fluoromethyl isopropyl sulfone, difluoromethylisopropyl sulfone, trifluoromethyl isopropyl sulfone, trifluoroethyln-propyl sulfone, trifluoroethyl isopropyl sulfone, pentafluoroethyln-propyl sulfone, pentafluoroethyl isopropyl sulfone, trifluoroethyln-butyl sulfone, trifluoroethyl t-butyl sulfone, pentafluoroethyln-butyl sulfone, and pentafluoroethyl t-butyl sulfone.

Preferred of these are dimethyl sulfone, ethyl methyl sulfone, diethylsulfone, n-propyl methyl sulfone, isopropyl methyl sulfone, n-butylmethyl sulfone, t-butyl methyl sulfone, monofluoromethyl methyl sulfone,difluoromethyl methyl sulfone, trifluoromethyl methyl sulfone,monofluoroethyl methyl sulfone, difluoroethyl methyl sulfone,trifluoroethyl methyl sulfone, pentafluoroethyl methyl sulfone, ethylmonofluoromethyl sulfone, ethyl difluoromethyl sulfone, ethyltrifluoromethyl sulfone, ethyl trifluoroethyl sulfone, ethylpentafluoroethyl sulfone, trifluoromethyl n-propyl sulfone,trifluoromethyl isopropyl sulfone, trifluoroethyl n-butyl sulfone,trifluoroethyl t-butyl sulfone, trifluoromethyl n-butyl sulfone,trifluoromethyl t-butyl sulfone, and the like, from the standpoint thatthese sulfone compounds have a high ionic conductivity and bring abouthigh input/output characteristics.

The amount of such a sulfone compound to be incorporated per 100% byvolume the nonaqueous solvent is preferably 0.3% by volume or more, andis preferably 80% by volume or less. So long as the amount thereof iswithin that range, it is easy to obtain the effect of improvingdurability such as cycle characteristics and storability. In addition,the viscosity of the nonaqueous electrolytic solution can be regulatedso as to be within an adequate range, and a decrease in electricalconductivity can be avoided. Furthermore, it is easy to avoid thetrouble that the nonaqueous-electrolyte secondary battery decreases incharge/discharge capacity retention when charged and discharged at ahigh current density. The amount of the sulfone compound to beincorporated is more preferably 0.5% by volume or more, even morepreferably 1% by volume or more, and is more preferably 75% by volume orless, even more preferably 70% by volume or less.

1-3. Aids

<Cyclic Carbonates Having Carbon-Carbon Unsaturated Bond>

In the nonaqueous electrolytic solution of the invention, a cycliccarbonate having a carbon-carbon unsaturated bond (hereinafter oftenreferred to simply as “unsaturated cyclic carbonate”) can be used inorder to form a coating film on the surface of the negative electrode ofthe nonaqueous-electrolyte battery to attain battery life prolongation.

The cyclic carbonate having a carbon-carbon unsaturated bond is notparticularly limited so long as the carbonate is a cyclic carbonatehaving a carbon-carbon unsaturated bond, and any desired carbonatehaving a carbon-carbon unsaturated bond can be used. Cyclic carbonateswhich have a substituent having an aromatic ring are also included inthe cyclic carbonate having a carbon-carbon unsaturated bond.

Examples of the unsaturated cyclic carbonate include vinylene carbonatecompounds, ethylene carbonate compounds substituted with one or morearomatic rings or substituents having a carbon-carbon unsaturated bond,phenyl carbonate compounds, vinyl carbonate compounds, and allycarbonate compounds.

Examples of the vinylene carbonate compounds include vinylene carbonate,methylvinylene carbonate, 4,5-dimethylvinylene carbonate, phenylvinylenecarbonate, 4,5-diphenylvinylene carbonate, vinylvinylene carbonate, andallylvinylene carbonate.

Examples of the ethylene carbonate compounds substituted with one ormore aromatic rings or substituents having a carbon-carbon unsaturatedbond include vinylethylene carbonate, 4,5-divinylethylene carbonate,phenylethylene carbonate, 4,5-diphenylethylene carbonate,ethynylethylene carbonate, and 4,5-diethynylethylene carbonate.

Preferred of these are the vinylene carbonate compounds and the ethylenecarbonates substituted with one or more aromatic rings or substituentshaving a carbon-carbon unsaturated bond. In particular, vinylenecarbonate, 4,5-diphenylvinylene carbonate, 4,5-dimethylvinylenecarbonate, vinylethylene carbonate, and ethynylethylene carbonate aremore suitable for use because these compounds form a stableinterface-protective coating film.

The molecular weight of such an unsaturated cyclic carbonate is notparticularly limited, and the carbonate may have any desired molecularweight unless the effects of the invention are considerably lessenedthereby. The molecular weight thereof is preferably 50-250. So long asthe unsaturated cyclic carbonate has a molecular weight within thisrange, it is easy to ensure the solubility of the unsaturated cycliccarbonate in the nonaqueous electrolytic solution and the effects of theinvention are apt to be sufficiently produced. The molecular weight ofthe unsaturated cyclic carbonate is more preferably 80 or higher, and ismore preferably 150 or less. Methods for producing the unsaturatedcyclic carbonate are not particularly limited, and the carbonate can beproduced by a known method selected at will.

One unsaturated cyclic carbonate may be used alone, or any desired twoor more unsaturated cyclic carbonates may be used in combination in anydesired proportion. The amount of the unsaturated cyclic carbonate to beincorporated is not particularly limited, and the carbonate may beincorporated in any desired amount unless the effects of the inventionare considerably lessened thereby. The amount of the unsaturated cycliccarbonate per 100% by mass the nonaqueous electrolytic solution ispreferably 0.001% by mass or more, more preferably 0.01% by mass ormore, even more preferably 0.1% by mass or more, especially preferably0.2% by mass or more, and is preferably 10% by mass or less, morepreferably 8% by mass or less, even more preferably 5% by mass or less.The range of the concentration of the unsaturated cyclic carbonate ispreferably 0.001-10% by mass, more preferably 0.001-8% by mass, evenmore preferably 0.001-5% by mass.

So long as the amount of the unsaturated cyclic carbonate is within thatrange, it is easy to produce the effect of sufficiently improving thecycle characteristics of the nonaqueous-electrolyte secondary battery.In addition, it is easy to avoid the trouble that the battery hasreduced high-temperature storability to evolve a gas in an increasedamount and decreases in discharge capacity retention.

<Fluorinated Unsaturated Cyclic Carbonates>

It is also preferred that a cyclic carbonate having one or moreunsaturated bonds and one or more fluorine atoms (hereinafter oftenreferred to simply as “fluorinated unsaturated cyclic carbonate”) shouldbe used as the fluorinated cyclic carbonate. The fluorinated unsaturatedcyclic carbonate is not particularly limited. Especially preferred arefluorinated unsaturated cyclic carbonates having one or two fluorineatoms.

Examples of the fluorinated unsaturated cyclic carbonate includevinylene carbonate derivatives and ethylene carbonate derivativessubstituted with one or more aromatic rings or substituents having acarbon-carbon unsaturated bond.

Examples of the vinylene carbonate derivatives include 4-fluorovinylenecarbonate, 4-fluoro-5-methylvinylene carbonate,4-fluoro-5-phenylvinylene carbonate, and 4,5-difluoroethylene carbonate.

Examples of the ethylene carbonate derivatives substituted with one ormore aromatic rings or substituents having a carbon-carbon unsaturatedbond include 4-fluoro-4-vinylethylene carbonate,4-fluoro-5-vinylethylene carbonate, 4,4-difluoro-4-vinylethylenecarbonate, 4,5-difluoro-4-vinylethylene carbonate, 4-fluoro-4,5-divinylethylene carbonate, 4,5-difluoro-4,5-divinylethylene carbonate,4-fluoro-4-phenylethylene carbonate, 4-fluoro-5-phenylethylenecarbonate, 4,4-difluoro-5-phenylethylene carbonate, and4,5-difluoro-4-phenylethylene carbonate.

The molecular weight of the fluorinated unsaturated cyclic carbonate isnot particularly limited, and the carbonate may have any desiredmolecular weight unless the effects of the invention are considerablylessened thereby. The molecular weight thereof is preferably 50-250. Solong as the fluorinated unsaturated cyclic carbonate has a molecularweight within this range, it is easy to ensure the solubility of thefluorinated cyclic carbonate in the nonaqueous electrolytic solution andthe effects of the invention are apt to be produced. Methods forproducing the fluorinated unsaturated cyclic carbonate are notparticularly limited, and the carbonate can be produced by a knownmethod selected at will. The molecular weight of this carbonate is morepreferably 80 or higher, and is more preferably 150 or less.

One fluorinated unsaturated cyclic carbonate may be used alone, or anydesired two or more fluorinated unsaturated cyclic carbonates may beused in combination in any desired proportion. The amount of thefluorinated unsaturated cyclic carbonate to be incorporated is notparticularly limited, and the carbonate may be incorporated in anydesired amount unless the effects of the invention are considerablylessened thereby. The amount of the fluorinated unsaturated cycliccarbonate per 100% by mass the nonaqueous electrolytic solution ispreferably 0.01% by mass or more, and is preferably 5% by mass or less.So long as the amount of the fluorinated unsaturated cyclic carbonate iswithin that range, it is easy to produce the effect of sufficientlyimproving the cycle characteristics of the nonaqueous-electrolytesecondary battery. In addition, it is easy to avoid the trouble that thebattery has reduced high-temperature storability to evolve a gas in anincreased amount and decreases in discharge capacity retention. Theamount of the fluorinated unsaturated cyclic carbonate to beincorporated is more preferably 0.1% by mass or more, even morepreferably 0.2% by mass or more, and is more preferably 4% by mass orless, even more preferably 3% by mass or less.

<Cyclic Sulfonic Acid Ester Compounds>

Cyclic sulfonic acid ester compounds usable in the nonaqueouselectrolytic solution of the invention are not particularly limited inthe kind thereof. However, compounds represented by general formula (2)are more preferred.

In the formula, R¹ and R² each independently represent an organic groupconfigured of atoms selected from the group consisting of carbon,hydrogen, nitrogen, oxygen, sulfur, phosphorus, and halogen atoms. R¹and R² each may contain an unsaturated bond together with —O—SO₂—.

It is preferred that R¹ and R² should be organic groups configured ofatoms comprising carbon, hydrogen, oxygen, and sulfur atoms. Inparticular, it is preferred that R¹ and R² each should be a hydrocarbongroup having 1-3 carbon atoms or an organic group having —O—SO₂—.

The molecular weight of such a cyclic sulfonic acid ester compound isnot particularly limited, and the ester may have any desired molecularweight unless the effects of the invention are considerably lessenedthereby. The molecular weight thereof is preferably 100-250. So long asthe cyclic sulfonic acid ester compound has a molecular weight withinthat range, it is easy to ensure the solubility of the cyclic sulfonicacid ester compound in the nonaqueous electrolytic solution and theeffects of the invention are apt to be produced. Methods for producingthe cyclic sulfonic acid ester compound are not particularly limited,and the ester compound can be produced by a known method selected atwill.

Examples of the compounds represented by general formula (2) include:sultone compounds such as

-   1,3-propane sultone,-   1-fluoro-1,3-propane sultone,-   2-fluoro-1,3-propanesultone,-   3-fluoro-1,3-propanesultone,-   1-methyl-1,3-propanesultone,-   2-methyl-1,3-propanesultone,-   3-methyl-1,3-propanesultone,-   1-propene-1,3-sultone,-   2-propene-1,3-sultone,-   1-fluoro-1-propene-1,3-sultone,-   2-fluoro-1-propene-1,3-sultone,-   3-fluoro-1-propene-1,3-sultone,-   1-fluoro-2-propene-1,3-sultone,-   2-fluoro-2-propene-1,3-sultone,-   3-fluoro-2-propene-1,3-sultone,-   1-methyl-1-propene-1,3-sultone,-   2-methyl-1-propene-1,3-sultone,-   3-methyl-1-propene-1,3-sultone,-   1-methyl-2-propene-1,3-sultone,-   2-methyl-2-propene-1,3-sultone,-   3-methyl-2-propene-1,3-sultone,-   1,4-butanesultone,-   1-fluoro-1,4-butanesultone,-   2-fluoro-1,4-butanesultone,-   3-fluoro-1,4-butanesultone,-   4-fluoro-1,4-butanesultone,-   1-methyl-1,4-butanesultone,-   2-methyl-1,4-butanesultone,-   3-methyl-1,4-butanesultone,-   4-methyl-1,4-butanesultone,-   1-butene-1,4-sultone,-   2-butene-1,4-sultone,-   3-butene-1,4-sultone,-   1-fluoro-1-butene-1,4-sultone,-   2-fluoro-1-butene-1,4-sultone,-   3-fluoro-1-butene-1,4-sultone,-   4-fluoro-1-butene-1,4-sultone,-   1-fluoro-2-butene-1,4-sultone,-   2-fluoro-2-butene-1,4-sultone,-   3-fluoro-2-butene-1,4-sultone,-   4-fluoro-2-butene-1,4-sultone,-   1-fluoro-3-butene-1,4-sultone,-   2-fluoro-3-butene-1,4-sultone,-   3-fluoro-3-butene-1,4-sultone,-   4-fluoro-3-butene-1,4-sultone,-   1-methyl-1-butene-1,4-sultone,-   2-methyl-1-butene-1,4-sultone,-   3-methyl-1-butene-1,4-sultone,-   4-methyl-1-butene-1,4-sultone,-   1-methyl-2-butene-1,4-sultone,-   2-methyl-2-butene-1,4-sultone,-   3-methyl-2-butene-1,4-sultone,-   4-methyl-2-butene-1,4-sultone,-   1-methyl-3-butene-1,4-sultone,-   2-methyl-3-butene-1,4-sultone,-   3-methyl-3-butene-1,4-sultone,-   4-methyl-3-butene-1,4-sultone,-   1,5-pentanesultone,-   1-fluoro-1,5-pentanesultone,-   2-fluoro-1,5-pentanesultone,-   3-fluoro-1,5-pentanesultone,-   4-fluoro-1,5-pentanesultone,-   5-fluoro-1,5-pentanesultone,-   1-methyl-1,5-pentanesultone,-   2-methyl-1,5-pentanesultone,-   3-methyl-1,5-pentanesultone,-   4-methyl-1,5-pentanesultone,-   5-methyl-1,5-pentanesultone,-   1-pentene-1,5-sultone,-   2-pentene-1,5-sultone,-   3-pentene-1,5-sultone,-   4-pentene-1,5-sultone,-   1-fluoro-1-pentene-1,5-sultone,-   2-fluoro-1-pentene-1,5-sultone,-   3-fluoro-1-pentene-1,5-sultone,-   4-fluoro-1-pentene-1,5-sultone,-   5-fluoro-1-pentene-1,5-sultone,-   1-fluoro-2-pentene-1,5-sultone,-   2-fluoro-2-pentene-1,5-sultone,-   3-fluoro-2-pentene-1,5-sultone,-   4-fluoro-2-pentene-1,5-sultone,-   5-fluoro-2-pentene-1,5-sultone,-   1-fluoro-3-pentene-1,5-sultone,-   2-fluoro-3-pentene-1,5-sultone,-   3-fluoro-3-pentene-1,5-sultone,-   4-fluoro-3-pentene-1,5-sultone,-   5-fluoro-3-pentene-1,5-sultone,-   1-fluoro-4-pentene-1,5-sultone,-   2-fluoro-4-pentene-1,5-sultone,-   3-fluoro-4-pentene-1,5-sultone,-   4-fluoro-4-pentene-1,5-sultone,-   5-fluoro-4-pentene-1,5-sultone,-   1-methyl-1-pentene-1,5-sultone,-   2-methyl-1-pentene-1,5-sultone,-   3-methyl-1-pentene-1,5-sultone,-   4-methyl-1-pentene-1,5-sultone,-   5-methyl-1-pentene-1,5-sultone,-   1-methyl-2-pentene-1,5-sultone,-   2-methyl-2-pentene-1,5-sultone,-   3-methyl-2-pentene-1,5-sultone,-   4-methyl-2-pentene-1,5-sultone,-   5-methyl-2-pentene-1,5-sultone,-   1-methyl-3-pentene-1,5-sultone,-   2-methyl-3-pentene-1,5-sultone,-   3-methyl-3-pentene-1,5-sultone,-   4-methyl-3-pentene-1,5-sultone,-   5-methyl-3-pentene-1,5-sultone,-   1-methyl-4-pentene-1,5-sultone,-   2-methyl-4-pentene-1,5-sultone,-   3-methyl-4-pentene-1,5-sultone,-   4-methyl-4-pentene-1,5-sultone, and-   5-methyl-4-pentene-1,5-sultone;-   sulfate compounds such as-   methylene sulfate,-   ethylene sulfate, and-   propylene sulfate;-   disulfonate compounds such as-   methylene methanedisulfonate and-   ethylene methanedisulfonate;-   nitrogen-containing compounds such as-   1,2,3-oxathiazolidine-2,2-dioxide,-   3-methyl-1,2,3-oxathiazolidine-2,2-dioxide,-   3H-1,2,3-oxathiazole-2,2-dioxide,-   5H-1,2,3-oxathiazole-2,2-dioxide,-   1,2,4-oxathiazolidine-2,2-dioxide,-   4-methyl-1,2,4-oxathiazolidine-2,2-dioxide,-   3H-1,2,4-oxathiazole-2,2-dioxide,-   5H-1,2,4-oxathiazole-2,2-dioxide,-   1,2,5-oxathiazolidine-2,2-dioxide,-   5-methyl-1,2,5-oxathiazolidine-2,2-dioxide,-   3H-1,2,5-oxathiazole-2,2-dioxide,-   5H-1,2,5-oxathiazole-2,2-dioxide,-   1,2,3-oxathiazinane-2,2-dioxide,-   3-methyl-1,2,3-oxathiazinane-2,2-dioxide,-   5,6-dihydro-1,2,3-oxathiazine-2,2-dioxide,-   1,2,4-oxathiazinane-2,2-dioxide,-   4-methyl-1,2,4-oxathiazinane-2,2-dioxide,-   5,6-dihydro-1,2,4-oxathiazine-2,2-dioxide,-   3,6-dihydro-1,2,4-oxathiazine-2,2-dioxide,-   3,4-dihydro-1,2,4-oxathiazine-2,2-dioxide,-   1,2,5-oxathiazinane-2,2-dioxide,-   5-methyl-1,2,5-oxathiazinane-2,2-dioxide,-   5,6-dihydro-1,2,5-oxathiazine-2,2-dioxide,-   3,6-dihydro-1,2,5-oxathiazine-2,2-dioxide,-   3,4-dihydro-1,2,5-oxathiazine-2,2-dioxide,-   1,2,6-oxathiazinane-2,2-dioxide,-   6-methyl-1,2,6-oxathiazinane-2,2-dioxide,-   5,6-dihydro-1,2,6-oxathiazine-2,2-dioxide,-   3,4-dihydro-1,2,6-oxathiazine-2,2-dioxide, and-   5,6-dihydro-1,2,6-oxathiazine-2,2-dioxide; and-   phosphorus-containing compounds such as-   1,2,3-oxathiaphoslane-2,2-oxide,-   3-methyl-1,2,3-oxathiaphoslane-2,2-oxide,-   3-methyl-1,2,3-oxathiaphoslane-2,2,3-trioxide,-   3-methoxy-1,2,3-oxathiaphoslane-2,2,3-trioxide,-   1,2,4-oxathiaphoslane-2,2-dioxide,-   4-methyl-1,2,4-oxathiaphoslane-2,2-dioxide,-   4-methyl-1,2,4-oxathiaphoslane-2,2,4-trioxide,-   4-methoxy-1,2,4-oxathiaphoslane-2,2,4-trioxide,-   1,2,5-oxathiaphoslane-2,2-dioxide,-   5-methyl-1,2,5-oxathiaphoslane-2,2-dioxide,-   5-methyl-1,2,5-oxathiaphoslane-2,2,5-trioxide,-   5-methoxy-1,2,5-oxathiaphoslane-2,2,5-trioxide,-   1,2,3-oxathiaphosphinane-2,2-dioxide,-   3-methyl-1,2,3-oxathiaphosphinane-2,2-dioxide,-   3-methyl-1,2,3-oxathiaphosphinane-2,2,3-trioxide,-   3-methoxy-1,2,3-oxathiaphosphinane-2,2,3-trioxide,-   1,2,4-oxathiaphosphinane-2,2-dioxide,-   4-methyl-1,2,4-oxathiaphosphinane-2,2-dioxide,-   4-methyl-1,2,4-oxathiaphosphinane-2,2,3-trioxide,-   4-methyl-1,5,2,4-dioxathiaphosphinane-2,4-dioxide,-   4-methoxy-1,5,2,4-dioxathiaphosphinane-2,4-dioxide,-   3-methoxy-1,2,4-oxathiaphosphinane-2,2,3-trioxide,-   1,2,5-oxathiaphosphinane-2,2-dioxide,-   5-methyl-1,2,5-oxathiaphosphinane-2,2-dioxide,-   5-methyl-1,2,5-oxathiaphosphinane-2,2,3-trioxide,-   5-methoxy-1,2,5-oxathiaphosphinane-2,2,3-trioxide,-   1,2,6-oxathiaphosphinane-2,2-dioxide,-   6-methyl-1,2,6-oxathiaphosphinane-2,2-dioxide,-   6-methyl-1,2,6-oxathiaphosphinane-2,2,3-trioxide, and-   6-methoxy-1,2,6-oxathiaphosphinane-2,2,3-trioxide.

Preferred of these from the standpoint of improving storability are1,3-propanesultone, 1-fluoro-1,3-propanesultone,2-fluoro-1,3-propanesultone, 3-fluoro-1,3-propanesultone,1-propene-1,3-sultone, 1-fluoro-1-propene-1,3-sultone,2-fluoro-1-propene-1,3-sultone, 3-fluoro-1-propene-1,3-sultone,1,4-butane sultone, methylene methanedisulfonate, and ethylenemethanedisulfonate. More preferred are 1,3-propanesultone,1-fluoro-1,3-propane sultone, 2-fluoro-1,3-propane sultone,3-fluoro-1,3-propanesultone, and 1-propene-1,3-sultone.

One cyclic sulfonic acid ester compound may be used alone, or anydesired two or more cyclic sulfonic acid ester compounds may be used incombination in any desired proportion. The amount of the cyclic sulfonicacid ester compound to be incorporated, based on the whole nonaqueouselectrolytic solution of the invention, is not limited, and the estercompound may be incorporated in any desired amount unless the effects ofthe invention are considerably lessened thereby. However, the estercompound is incorporated in a concentration which is generally 0.001% bymass or more, preferably 0.1% by mass or more, more preferably 0.3% bymass or more, based on the nonaqueous electrolytic solution of theinvention, and is generally 10% by mass or less, preferably 5% by massor less, more preferably 3% by mass or less. When the concentrationthereof satisfies that range, the effects concerning outputcharacteristics, load characteristics, low-temperature characteristics,cycle characteristics, high-temperature storability, etc. are moreimproved.

<Compounds Having Cyano Group>

Compounds which have one or more cyano groups and are usable in thenonaqueous electrolytic solution of the invention are not particularlylimited in the kind thereof so long as the compounds each have one ormore cyano groups in the molecule. However, compounds represented bygeneral formula (3) are more preferred.

(In the formula, T represents an organic group configured of atomsselected from the group consisting of carbon, hydrogen, nitrogen,oxygen, sulfur, phosphorus, and halogen atoms, and U is a V-valentorganic group which has 1-10 carbon atoms and may have a substituent. Vis an integer of 1 or larger. When V is 2 or larger, the T's may be thesame or different.)

The molecular weight of such a compound having one or more cyano groupsis not particularly limited, and the compound may have any desiredmolecular weight unless the effects of the invention are considerablylessened thereby. The molecular weight thereof is preferably 50 orhigher, more preferably 80 or higher, even more preferably 100 orhigher, and is preferably 200 or less. So long as the compound havingone or more cyano groups has a molecular weight within that range, it iseasy to ensure the solubility of this compound in the nonaqueouselectrolytic solution and the effects of the invention are apt to beproduced. Methods for producing the compounds having one or more cyanogroups are not particularly limited, and the compounds can be producedby a known method selected at will.

Examples of the compounds represented by general formula (3) include:

-   compounds having one cyano group, such as-   acetonitrile,-   propionitrile,-   butyronitrile,-   isobutyronitrile,-   valeronitrile,-   isovaleronitrile,-   lauronitrile,-   2-methylbutyronitrile,-   trimethylacetonitrile,-   hexanenitrile,-   cyclopentanecarbonitrile,-   cyclohexanecarbonitrile,-   acrylonitrile,-   methacrylonitrile,-   crotononitrile,-   3-methylcrotononitrile,-   2-methyl-2-butenenitrile,-   2-pentenenitrile,-   2-methyl-2-pentenenitrile,-   3-methyl-2-pentenenitrile,-   2-hexenenitrile,-   fluoroacetonitrile,-   difluoroacetonitrile,-   trifluoroacetonitrile,-   2-fluoropropionitrile,-   3-fluoropropionitrile,-   2,2-difluoropropionitrile,-   2,3-difluoropropionitrile,-   3,3-difluoropropionitrile,-   2,2,3-trifluoropropionitrile,-   3,3,3-trifluoropropionitrile,-   3,3′-oxydipropionitrile,-   3,3′-thiodipropionitrile,-   1,2,3-propanetricarbonitrile,-   1,3,5-pentanetricarbonitrile, and-   pentafluoropropionitrile;-   compounds having two cyano groups, such as-   malononitrile,-   succinonitrile,-   glutaronitrile,-   adiponitrile,-   pimelonitrile,-   suberonitrile,-   azelanitrile,-   sebaconitrile,-   undecanedinitrile,-   dodecanedinitrile,-   methylmalononitrile,-   ethylmalononitrile,-   isopropylmalononitrile,-   tert-butylmalononitrile,-   methylsuccinonitrile,-   2,2-dimethylsuccinonitrile,-   2,3-dimethylsuccinonitrile,-   trimethylsuccinonitrile,-   tetramethylsuccinonitrile,-   3,3′-(ethylenedioxy)dipropionitrile, and-   3,3′-(ethylenedithio)dipropionitrile;-   compounds having three cyano groups, such as-   1,2,3-tris(2-cyanoethoxy)propane and-   tris(2-cyanoethyl)amine;-   cyanate compounds such as-   methyl cyanate,-   ethyl cyanate,-   propyl cyanate,-   butyl cyanate,-   pentyl cyanate,-   hexyl cyanate, and-   heptyl cyanate;-   sulfur-containing compounds such as-   methyl thiocyanate,-   ethyl thiocyanate,-   propyl thiocyanate,-   butyl thiocyanate,-   pentyl thiocyanate,-   hexyl thiocyanate,-   heptyl thiocyanate,-   methanesulfonyl cyanide,-   ethanesulfonyl cyanide,-   propanesulfonyl cyanide,-   butanesulfonyl cyanide,-   pentanesulfonyl cyanide,-   hexanesulfonyl cyanide,-   heptanesulfonyl cyanide,-   methyl sulfurocyanidate,-   ethyl sulfurocyanidate,-   propyl sulfurocyanidate,-   butyl sulfurocyanidate,-   pentyl sulfurocyanidate,-   hexyl sulfurocyanidate, and-   heptyl sulfurocyanidate; and-   phosphorus-containing compounds such as-   cyanodimethylphosphine,-   cyanodimethylphosphine oxide,-   methyl cyanomethylphosphinate,-   the methyl ester of cyanomethylphosphinous acid,-   dimethylphosphinic cyanide,-   dimethylphosphinous cyanide,-   dimethyl cyanophosphonate,-   the dimethyl ester of cyanophosphonous acid,-   cyanomethyl methylphosphonate,-   the cyanomethyl ester of methylphosphonous acid,-   cyanodimethyl phosphate, and-   cyanodimethyl phosphite.

Preferred of these, from the standpoint of improving storability, areacetonitrile, propionitrile, butyronitrile, isobutyronitrile,valeronitrile, isovaleronitrile, lauronitrile, crotononitrile,3-methylcrotononitrile, malononitrile, succinonitrile, glutaronitrile,adiponitrile, pimelonitrile, suberonitrile, azelanitrile, sebaconitrile,undecanedinitrile, and dodecanedinitrile. More preferred are compoundshaving two cyano groups, such as malononitrile, succinonitrile,glutaronitrile, adiponitrile, pimelonitrile, suberonitrile,azelanitrile, sebaconitrile, undecanedinitrile, and dodecanedinitrile.

One compound having one or more cyano groups may be used alone, or anydesired two or more compounds having one or more cyano groups may beused in combination in any desired proportion. The amount of thecompound having one or more cyano groups to be incorporate, based on thewhole nonaqueous electrolytic solution of the invention, is not limited,and the compound may be incorporated in any desired amount unless theeffects of the invention are considerably lessened thereby. However, thecompound is incorporated in a concentration which is generally 0.001% bymass or higher, preferably 0.1% by mass or higher, more preferably 0.3%by mass or higher, based on the nonaqueous electrolytic solution of theinvention, and is generally 10% by mass or less, preferably 5% by massor less, more preferably 3% by mass or less. When the concentrationthereof satisfies that range, the effects concerning outputcharacteristics, load characteristics, low-temperature characteristics,cycle characteristics, high-temperature storability, etc. are moreimproved.

<Diisocyanate Compounds>

Diisocyanate compounds usable in the nonaqueous electrolytic solution ofthe invention are not particularly limited so long as the compounds eachhave two isocyanate groups in the molecule. However, diisocyanatecompounds represented by the following general formula (4) arepreferred.

[Chem. 3]NCO—X—NCO  (4)(In the formula, X is a hydrocarbon group which has 1-16 carbon atomsand may have been substituted with fluorine.)

In general formula (4), X is a hydrocarbon group which has 1-16 carbonatoms and may have been substituted with fluorine. The number of carbonatoms of X is preferably 2 or greater, more preferably 3 or greater,especially preferably 4 or greater, and is preferably 14 or less, morepreferably 12 or less, especially preferably 10 or less, most preferably8 or less. The kind of X is not particularly limited so long as X is ahydrocarbon group. Although X may be any of an aliphatic chain alkylenegroup, an aliphatic cyclic alkylene group, and anaromatic-ring-containing hydrocarbon group, it is preferred that Xshould be an aliphatic chain alkylene group or an aliphatic cyclicalkylene group.

Examples of the diisocyanates in the invention include:

linear polymethylene diisocyanates such as ethylene diisocyanate,trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylenediisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate,octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylenediisocyanate, and tetradecamethylene diisocyanate; branched alkylenediisocyanates such as methyltetramethylene diisocyanate,dimethyltetramethylene diisocyanate, trimethyltetramethylenediisocyanate, methylhexamethylene diisocyanate, dimethylhexamethylenediisocyanate, trimethylhexamethylene diisocyanate, methyloctamethylenediisocyanate, dimethyloctamethylene diisocyanate, andtrimethyloctamethylene diisocyanate; diisocyanatoalkenes such as1,4-diisocyanato-2-butene, 1,5-diisocyanato-2-pentene,1,5-diisocyanato-3-pentene, 1,6-diisocyanato-2-hexene,1,6-diisocyanato-3-hexene, 1,8-diisocyanato-2-octene,1,8-diisocyanato-3-octene, and 1,8-diisocyanato-4-octene;fluorine-substituted diisocyanatoalkanes such as1,3-diisocyanato-2-fluoropropane, 1,3-diisocyanato-2,2-difluoropropane,1,4-diisocyanato-2-fluorobutane, 1,4-diisocyanato-2,2-difluorobutane,1,4-diisocyanato-2,3-difluorobutane, 1,6-diisocyanato-2-fluorohexane,1,6-diisocyanato-3-fluorohexane, 1,6-diisocyanato-2,2-difluorohexane,1,6-diisocyanato-2,3-difluorohexane,1,6-diisocyanato-2,4-difluorohexane,1,6-diisocyanato-2,5-difluorohexane,1,6-diisocyanato-3,3-difluorohexane,1,6-diisocyanato-3,4-difluorohexane, 1,8-diisocyanato-2-fluorooctane,1,8-diisocyanato-3-fluorooctane, 1,8-diisocyanato-4-fluorooctane,1,8-diisocyanato-2,2-difluorooctane,1,8-diisocyanato-2,3-difluorooctane,1,8-diisocyanato-2,4-difluorooctane,1,8-diisocyanato-2,5-difluorooctane,1,8-diisocyanato-2,6-difluorooctane, and1,8-diisocyanato-2,7-difluorooctane; cycloalkane-ring-containingdiisocyanates such as 1,2-diisocyanatocyclopentane,1,3-diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane,1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane,1,2-bis(isocyanatomethyl)cyclohexane,1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane2,2′-diisocyanate, dicyclohexylmethane 2,4′-diisocyanate,dicyclohexylmethane 3,3′-diisocyanate, and dicyclohexylmethane4,4′-diisocyanate; and aromatic-ring-containing diisocyanates such as1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylenediisocyanate, tolylene 2,3-diisocyanate, tolylene 2,4-diisocyanate,tolylene 2,5-diisocyanate, tolylene 2,6-diisocyanate, tolylene3,4-diisocyanate, tolylene 3,5-diisocyanate,1,2-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethypbenzene,1,4-bis(isocyanatomethyl)benzene, 2,4-diisocyanatobiphenyl,2,6-diisocyanatobiphenyl, 2,2′-diisocyanatobiphenyl,3,3′-diisocyanatobiphenyl, 4,4′-diisocyanato-2-methylbiphenyl,4,4′-diisocyanato-3-methylbiphenyl,4,4′-diisocyanato-3,3′-dimethylbiphenyl,4,4′-diisocyanatodiphenylmethane,4,4′-diisocyanato-2-methyldiphenylmethane,4,4′-diisocyanato-3-methyldiphenylmethane,4,4′-diisocyanato-3,3′-dimethyldiphenylmethane,1,5-diisocyanatonaphthalene, 1,8-diisocyanatonaphthalene,2,3-diisocyanatonaphthalene, 1,5-bis(isocyanatomethyl)naphthalene,1,8-bis(isocyanatomethyl)naphthalene, and2,3-bis(isocyanatomethyl)naphthalene.

Preferred of these are:

linear polymethylene diisocyanates such as ethylene diisocyanate,trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylenediisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate,octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylenediisocyanate, and tetradecamethylene diisocyanate; branched alkylenediisocyanates such as methyltetramethylene diisocyanate,dimethyltetramethylene diisocyanate, trimethyltetramethylenediisocyanate, methylhexamethylene diisocyanate, dimethylhexamethylenediisocyanate, trimethylhexamethylene diisocyanate, methyloctamethylenediisocyanate, dimethyloctamethylene diisocyanate, andtrimethyloctamethylene diisocyanate; and cycloalkane-ring-containingdiisocyanates such as 1,2-diisocyanato cyclopentane,1,3-diisocyanatocyclopentane, 1,2-diisocyanatocyclohexane,1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane,1,2-bis(isocyanatomethyl)cyclohexane,1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane2,2′-diisocyanate, dicyclohexylmethane 2,4′-diisocyanate,dicyclohexylmethane 3,3′-diisocyanate, and dicyclohexylmethane4,4′-diisocyanate.

Especially preferred of these are:

a linear polymethylene diisocyanate selected from tetramethylenediisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate,heptamethylene diisocyanate, and octamethylene diisocyanate; and acycloalkane-ring-containing diisocyanate selected from1,2-diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane,1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane,1,4-diisocyanatocyclohexane, 1,2-bis(isocyanatomethyl)cyclohexane,1,3-bis(isocyanatomethyl)cyclohexane,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane2,2′-diisocyanate, dicyclohexylmethane 2,4′-diisocyanate,dicyclohexylmethane 3,3′-diisocyanate, and dicyclohexylmethane4,4′-diisocyanate.

One of those diisocyanates in the invention may be used alone, or anydesired two or more thereof may be used in combination in any desiredproportion.

The content of such a diisocyanate usable in the nonaqueous electrolyticsolution of the invention, based on the whole nonaqueous electrolyticsolution, is usually 0.001% by mass or higher, preferably 0.01% by massor higher, more preferably 0.1% by mass or higher, even more preferably0.3% by mass or higher, and is usually 5% by mass or less, preferably4.0% by mass or less, more preferably 3.0% by mass or less, even morepreferably 2% by mass or less. When the content thereof is within thatrange, durability such as cycle characteristics and storability can beimproved and the effects of the invention can be sufficiently produced.

<Overcharge Inhibitor>

An overcharge inhibitor can be used in the nonaqueous electrolyticsolution of the invention in order to effectively inhibit thenonaqueous-electrolyte secondary battery from bursting or firing whenbrought into an overcharged state or the like.

Examples of the overcharge inhibitor include: aromatic compounds such asbiphenyl, alkylbiphenyls, terphenyl, partly hydrogenated terphenyls,cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, anddibenzofuran; products of partial fluorination of these aromaticcompounds, such as 2-fluorobiphenyl, o-cyclohexylfluorobenzene, andp-cyclohexylfluorobenzene; and fluorine-containing anisole compoundssuch as 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole,and 3,5-difluoroanisole. Preferred of these are aromatic compounds suchas biphenyl, alkylbiphenyls, terphenyl, partly hydrogenated terphenyls,cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, anddibenzofuran. One of these may be used alone, or two or more thereof maybe used in combination. In the case where two or more compounds are usedin combination, the following combinations are especially preferred fromthe standpoint of a balance between overcharge-preventive properties andhigh-temperature storability: a combination of cyclohexylbenzene witht-butylbenzene or t-amylbenzene; and a combination of at least onemember selected from aromatic compounds containing no oxygen, such asbiphenyl, alkylbiphenyls, terphenyl, partly hydrogenated terphenyls,cyclohexylbenzene, t-butylbenzene, and t-amylbenzene, with at least onemember selected from oxygen-containing aromatic compounds such asdiphenyl ether and dibenzofuran.

The amount of the overcharge inhibitor to be incorporated is notparticularly limited, and the overcharge inhibitor may be incorporatedin any desired amount unless the effects of the invention areconsiderably lessened thereby. The amount of the overcharge inhibitor ispreferably 0.1-5% by mass per 100% by mass the nonaqueous electrolyticsolution. So long as the amount thereof is within that range, it is easyto sufficiently produce the effect of the overcharge inhibitor and it iseasy to avoid the trouble that battery characteristics includinghigh-temperature storability decrease. The amount of the overchargeinhibitor is more preferably 0.2% by mass or more, even more preferably0.3% by mass or more, especially preferably 0.5% by mass or more, and ismore preferably 3% by mass or less, even more preferably 2% by mass orless.

<Other Aids>

Other known aids can be used in the nonaqueous electrolytic solution ofthe invention. Examples of the other aids include: carbonate compoundssuch as erythritane carbonate, spiro-bis-dimethylene carbonate, andmethoxyethyl methyl carbonate; carboxylic acid anhydrides such assuccinic anhydride, glutaric anhydride, maleic anhydride, citraconicanhydride, glutaconic anhydride, itaconic anhydride, diglycolicanhydride, cyclohexanedicarboxylic anhydride,cyclopentanetetracarboxylic dianhydride, and phenylsuccinic anhydride;spiro compounds such as 2,4,8,10-tetraoxaspiro[5.5]undecane and3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane; sulfur-containingcompounds such as ethylene sulfite, methyl fluorosulfonate, ethylfluorosulfonate, methyl methanesulfonate, ethyl methanesulfonate,busulfan, sulfolene, ethylene sulfate, vinylene sulfate, diphenylsulfone, N,N-dimethylmethane sulfonamide, andN,N-diethylmethanesulfonamide; nitrogen-containing compounds such as1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone,3-methyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, andN-methylsuccinimide; hydrocarbon compounds such as heptane, octane,nonane, decane, and cycloheptane; fluorine-containing aromatic compoundssuch as fluorobenzene, difluorobenzene, hexafluorobenzene, andbenzotrifluoride; and silane compounds such as tris(trimethylsilyl)borate, tris(trimethoxysilyl) borate, tris(trimethylsilyl) phosphate,tris(trimethoxysilyl) phosphate, dimethoxyaluminoxytrimethoxysilane,diethoxyaluminoxytriethoxysilane, dipropoxyaluminoxytriethoxysilane,dibutoxyaluminoxytrimethoxysilane, dibutoxyaluminoxytriethoxysilane,titanium tetrakis(trimethylsiloxide), and titaniumtetrakis(triethylsiloxide). One of these aids may be used alone, or twoor more thereof may be used in combination. By adding these aids,capacity retentivity after high-temperature storage and cyclecharacteristics can be improved.

The amount of the other aids to be incorporated is not particularlylimited, and the other aids may be incorporated in any desired amountunless the effects of the invention are considerably lessened thereby.The amount of the other aids is preferably 0.01-5% by mass per 100% bymass the nonaqueous electrolytic solution. So long as the amount thereofis within that range, it is easy to sufficiently produce the effects ofthe other aids and it is easy to avoid the trouble that batterycharacteristics including high-load discharge characteristics decrease.The amount of the other aids to be incorporated is more preferably 0.1%by mass or more, even more preferably 0.2% by mass or more, and is morepreferably 3% by mass or less, even more preferably 1% by mass or less.

The nonaqueous electrolytic solution described above includes thenonaqueous electrolytic solution present in inner parts of thenonaqueous-electrolyte battery according to the invention. Specifically,the invention includes: the nonaqueous electrolytic solution present ina nonaqueous-electrolyte battery obtained by separately synthesizingconstituent elements for a nonaqueous electrolytic solution, such as alithium salt, a solvent, and aids, preparing the nonaqueous electrolyticsolution from the substantially separate constituent elements, andintroducing the nonaqueous electrolytic solution into a batteryseparately assembled by the method which will be described later. Theinvention further includes: the case in which constituent elements for anonaqueous electrolytic solution of the invention are separatelyintroduced into a battery and mixed together within the battery tothereby obtain the same composition as the nonaqueous electrolyticsolution of the invention; and the case in which a compound serving as acomponent of a nonaqueous electrolytic solution of the invention isgenerated within the nonaqueous-electrolyte battery to obtain the samecomposition as the nonaqueous electrolytic solution of the invention.

2. Nonaqueous-Electrolyte Secondary Battery

The nonaqueous-electrolyte secondary battery of the invention includes:a negative electrode and a positive electrode which are capable ofoccluding and releasing ions; and the nonaqueous electrolytic solutionof the invention.

<2-1. Battery Configuration>

The nonaqueous-electrolyte secondary battery of the invention has thesame configuration as conventionally known nonaqueous-electrolytesecondary batteries, except for the negative electrode and thenonaqueous electrolytic solution. Usually, the battery of the inventionhas a configuration obtained by superposing a positive electrode and anegative electrode through a porous film (separator) impregnated withthe nonaqueous electrolytic solution of the invention and disposing thestack in a case (outer case). Consequently, the shape of thenonaqueous-electrolyte secondary battery of the invention is notparticularly limited, and may be any of cylindrical, prismatic, laminatetype, coin type, large-size, and other shapes.

<2-2. Nonaqueous Electrolyte Solution>

As the nonaqueous electrolytic solution, use is made of the nonaqueouselectrolytic solution of the invention described above. Incidentally, ablend of the nonaqueous electrolytic solution of the invention withanother nonaqueous electrolytic solution can be used so long as use ofthis blend does not depart from the spirit of the invention.

<2-3. Negative Electrode>

The negative electrode includes a current collector and anegative-electrode active-material layer disposed thereon. Thenegative-electrode active material is described below.

The negative-electrode active material is not particularly limited solong as the active material is capable of electrochemically occludingand releasing lithium ions. Examples thereof include a carbonaceousmaterial, an alloy material, and a lithium-containing composite metaloxide material. One of these materials may be used alone, or any desiredtwo or more thereof may be used in combination in any desiredproportion.

<2-3-1. Carbonaceous Material>

The carbonaceous material to be used as a negative-electrode activematerial preferably is a material selected from:

(1) natural graphites;

(2) carbonaceous materials obtained by subjecting artificialcarbonaceous substances and artificial graphitic substances to a heattreatment at a temperature in the range of 400-3,200° C. one or moretimes;

(3) carbonaceous materials giving a negative-electrode active-materiallayer which is composed of at least two carbonaceous substancesdiffering in crystallinity and/or has an interface where at least twocarbonaceous substances differing in crystallinity are in contact witheach other; and(4) carbonaceous materials giving a negative-electrode active-materiallayer which is composed of at least two carbonaceous substancesdiffering in orientation and/or has an interface where at least twocarbonaceous substances differing in orientation are in contact witheach other.This is because this carbonaceous material brings about a satisfactorybalance between initial irreversible capacity and high-current-densitycharge/discharge characteristics. One of the carbonaceous materials (1)to (4) may be used alone, or any desired two or more thereof may be usedin combination in any desired proportion.

Examples of the artificial carbonaceous substances and artificialgraphitic substances in (2) above include natural graphites, coal coke,petroleum coke, coal pitch, petroleum pitch, carbonaceous substancesobtained by oxidizing these pitches, needle coke, pitch coke, carbonmaterials obtained by partly graphitizing these cokes, products of thepyrolysis of organic substances, such as furnace black, acetylene black,and pitch-derived carbon fibers, organic substances capable ofcarbonization and products of the carbonization thereof, or solutionsobtained by dissolving any of such organic substances capable ofcarbonization in a low-molecular organic solvent, e.g., benzene,toluene, xylene, quinoline, or n-hexane, and products of thecarbonization of these solutions.

<2-3-2. Configuration and Properties of Carbonaceous Negative Electrodeand Method for Preparation Thereof>

With respect to the properties of a carbonaceous material, the negativeelectrode containing the carbonaceous material, techniques for electrodeformation, the current collector, and the nonaqueous-electrolytesecondary battery, it is desirable that any one or more of the following(1) to (13) should be simultaneously satisfied.

(1) X-Ray Parameter

The carbonaceous material preferably has a value of d (interplanarspacing) for the lattice planes (002), as determined by X-raydiffractometry in accordance with the method of the Japan Society forPromotion of Scientific Research, of generally 0.335-0.340 nm,especially 0.335-0.338 nm, in particular 0.335-0.337 nm. The crystallitesize (Lc) thereof as determined by X-ray diffractometry in accordancewith the method of the Japan Society for Promotion of ScientificResearch is generally 1.0 nm or larger, preferably 1.5 nm or larger,especially preferable 2 nm or larger.

(2) Volume-Average Particle Diameter

The volume-average particle diameter of the carbonaceous material, interms of volume-average particle diameter (median diameter) asdetermined by the laser diffraction/scattering method, is generally 1 μmor more, preferably 3 μm or more, more preferably 5 μm or more,especially preferably 7 μm or more, and is generally 100 μm or less,preferably 50 μm or less, more preferably 40 μm or less, even morepreferably 30 μm or less, especially preferably 25 μm or less. When thevolume-average particle diameter thereof is less than that range, thereare cases where irreversible capacity increases, leading to a loss ininitial battery capacity. When the volume-average particle diameterthereof exceeds that range, there are cases where such a carbonaceousmaterial is undesirable from the standpoint of battery productionbecause an uneven coating surface is apt to result when an electrode isproduced through coating fluid application.

Volume-average particle diameter is determined by dispersing the carbonpowder in a 0.2% by mass aqueous solution (about 10 mL) ofpoly(oxyethylene(20)) sorbitan monolaurate as a surfactant and examiningthe dispersion with a laser diffraction/scattering type particle sizedistribution analyzer (LA-700, manufactured by HORIBA, Ltd.). The mediandiameter determined through this measurement is defined as thevolume-average particle diameter of the carbonaceous material accordingto the invention.

(3) Raman R Value, Raman Half-Value Width

The Raman R value of the carbonaceous material as determined by theargon ion laser Raman spectroscopy is generally 0.01 or higher,preferably 0.03 or higher, more preferably 0.1 or higher, and isgenerally 1.5 or less, preferably 1.2 or less, more preferably 1 orless, especially preferably 0.5 or less.

When the Raman R value thereof is less than that range, there are caseswhere the surface of the particles has too high crystallinity and thenumber of intercalation sites into which lithium comes withcharge/discharge decreases. Namely, there are cases where thecarbonaceous material decreases in suitability for charge. In addition,there are cases where when a coating fluid containing the carbonaceousmaterial is applied to a current collector and the resultant coating ispressed to heighten the density of the negative electrode, then thecrystals are apt to orient in directions parallel to the electrode plateand this leads to a decrease in load characteristics. On the other hand,when the Raman R value thereof exceeds that range, there are cases wherethe surface of the particles has reduced crystallinity and enhancedreactivity with the nonaqueous electrolytic solution and this leads to adecrease in efficiency and enhanced gas evolution.

The Raman half-value width around 1,580 cm⁻¹ of the carbonaceousmaterial is not particularly limited. However, the half-value widththereof is generally 10 cm⁻¹ or more, preferably 15 cm⁻¹ or more, and isgenerally 100 cm⁻¹ or less, preferably 80 cm⁻¹ or less, more preferably60 cm⁻¹ or less, especially preferably 40 cm⁻¹ or less.

When the Raman half-value width thereof is less than that range, thereare cases where the surface of the particles has too high crystallinityand the number of intercalation sites into which lithium comes withcharge/discharge decreases. Namely, there are cases where thecarbonaceous material decreases in suitability for charge. In addition,there are cases where when a coating fluid containing the carbonaceousmaterial is applied to a current collector and the resultant coating ispressed to heighten the density of the negative electrode, then thecrystals are apt to orient in directions parallel to the electrode plateand this leads to a decrease in load characteristics. On the other hand,when the Raman half-value width thereof exceeds that range, there arecases where the surface of the particles has reduced crystallinity andenhanced reactivity with the nonaqueous electrolytic solution and thisleads to a decrease in efficiency and enhanced gas evolution.

The examination for Raman spectrum is made with a Raman spectrometer(Raman spectrometer manufactured by Japan Spectroscopic Co., Ltd.). Inthe examination, a sample is charged into a measuring cell by causingthe sample to fall naturally into the cell and the surface of the samplein the cell is irradiated with argon ion laser light while rotating thecell in a plane perpendicular to the laser light. The Raman spectrumobtained is examined for the intensity IA of a peak PA around 1,580 cm⁻¹and the intensity IB of a peak PB around 1,360 cm⁻¹. The ratio betweenthese intensities R(R=IB/IA) is calculated. The Raman R value calculatedthrough this examination is defined as the Raman R value of thecarbonaceous material according to the invention. Furthermore, thehalf-value width of the peak PA around 1,580 cm⁻¹ in the Raman spectrumobtained is measured, and this value is defined as the Raman half-valuewidth of the carbonaceous material according to the invention.

Conditions for the Raman spectroscopy are as follows.

Wavelength of argon ion laser: 514.5 nm

Laser power on sample: 15-25 mW

Resolution: 10-20 cm⁻¹

Examination range: 1,100 cm⁻¹ to 1,730 cm⁻¹

Analysis for Raman R value and Raman half-value width: backgroundprocessing

Smoothing: simple average; convolution, 5 points

(4) BET Specific Surface Area

The BET specific surface area of the carbonaceous material, in terms ofthe value of specific surface area as determined by the BET method, isgenerally 0.1 m²·g⁻¹ or larger, preferably 0.7 m²·g⁻¹ or larger, morepreferably 1.0 m²·g⁻¹ or larger, especially preferably 1.5 m²·g⁻¹ orlarger, and is generally 100 m²·g⁻¹ or smaller, preferably 25 m²·g⁻¹ orsmaller, more preferably 15 m²·g⁻¹ or smaller, especially preferably 10m²·g⁻¹ or smaller.

In case where the BET specific surface area thereof is less than thatrange, this carbonaceous material, when used as a negative-electrodematerial, is less apt to accept lithium during charge and lithiumdeposition is apt to occur on the electrode surface. Namely, there isthe possibility of resulting in a decrease in stability. On the otherhand, when the BET specific surface area thereof exceeds that range,there are cases where this carbonaceous material, when used as anegative-electrode material, is apt to have increased reactivity withthe nonaqueous electrolytic solution to cause enhanced gas evolution,making it difficult to give a preferred battery.

The determination of specific surface area by the BET method is madewith a surface area meter (a fully automatic surface area measuringapparatus manufactured by Ohkura Riken Co., Ltd.) by preliminarilydrying a sample at 350° C. for 15 minutes in a nitrogen stream and thenmeasuring the specific surface area thereof by the gas-flowing nitrogenadsorption BET one-point method using a nitrogen/helium mixture gasprecisely regulated so as to have a nitrogen pressure of 0.3 relative toatmospheric pressure. The specific surface area determined through thismeasurement is defined as the BET specific surface area of thecarbonaceous material according to the invention.

(5) Roundness

When the carbonaceous material is examined for roundness as an index tothe degree of sphericity thereof, the roundness thereof is preferablywithin the range shown below. Roundness is defined by “Roundness=(lengthof periphery of equivalent circle having the same area as projectedparticle shape)/(actual length of periphery of projected particleshape)”. When a particle has a roundness of 1, this particletheoretically is a true sphere.

The closer to 1 the roundness of carbonaceous-material particles havinga particle diameter in the range of 3-40 μm, the more the particles aredesirable. The roundness of the particles is desirably 0.1 or higher,preferably 0.5 or higher, more preferably 0.8 or higher, even morepreferably 0.85 or higher, especially preferably 0.9 or higher.

The higher the roundness, the more the high-current-densitycharge/discharge characteristics are improved. Consequently, when thecarbonaceous-material particles have a roundness less than that range,there are cases where the negative-electrode active material has reducedsuitability for loading and has enhanced interparticle resistance,resulting in a decrease in short-time high-current-densitycharge/discharge characteristics.

Roundness is determined with a flow type particle image analyzer (FPIA,manufactured by Sysmex Industrial Corp.). About 0.2 g of a sample isdispersed in a 0.2% by mass aqueous solution (about 50 mL) ofpoly(oxyethylene(20)) sorbitan monolaurate as a surfactant, and anultrasonic wave of 28 kHz is propagated to the dispersion for 1 minuteat an output of 60 W. Thereafter, particles having a particle diameterin the range of 3-40 μm are examined with the analyzer having adetection range set at 0.6-400 μm. The roundness determined through thismeasurement is defined as the roundness of the carbonaceous materialaccording to the invention.

Methods for improving roundness are not particularly limited. However, acarbonaceous material in which the particles have been rounded by arounding treatment is preferred because this material gives an electrodein which the interstices among particles are uniform in shape. Examplesof the rounding treatment include: a method in which shear force orcompressive force is applied to thereby mechanically make the shape ofthe particles close to sphere; and a method of mechanical/physicaltreatment in which fine particles are aggregated into particles by meansof the bonding force of either a binder or the fine particlesthemselves.

(6) Tap Density

The tap density of the carbonaceous material is generally 0.1 g·cm⁻³ orhigher, preferably 0.5 g·cm⁻³ or higher, more preferably 0.7 g·cm⁻³ orhigher, especially preferably 1 g·cm⁻³ or higher, and is preferably 2g·cm⁻³ or less, more preferably 1.8 g·cm⁻³ or less, especiallypreferably 1.6 g·cm⁻³ or less.

When the tap density thereof is less than that range, there are caseswhere this carbonaceous material, when used in a negative electrode, isless apt to attain an increased loading density, making it impossible toobtain a high-capacity battery. When the tap density thereof exceedsthat range, there are cases where the amount of interparticleinterstices in the electrode is too small and, hence, electricalconductivity among the particles is less apt to be ensured, making itdifficult to obtain preferred battery characteristics.

Tap density is determined by dropping a sample through a sieve having anopening size of 300 μm into a 20-cm³ tapping cell to fill the cell withthe sample up to the brim, subsequently conducting a tapping operation1,000 times over a stroke length of 10 mm using a powder densimeter(e.g., Tap Denser, manufactured by Seishin Enterprise Co., Ltd.), andcalculating the tap density from the resultant volume of the sample andthe weight thereof. The tap density calculated through this measurementis defined as the tap density of the carbonaceous material according tothe invention.

(7) Orientation Ratio

The orientation ratio of the carbonaceous material is generally 0.005 orgreater, preferably 0.01 or greater, more preferably 0.015 or greater,and is generally 0.67 or less. When the orientation ratio thereof isless than that range, there are cases where high-densitycharge/discharge characteristics decrease. The upper limit of that rangeis a theoretical upper limit of the orientation ratio of carbonaceousmaterials.

Orientation ratio is determined by X-ray diffractometry after a sampleis molded by compaction. A molded object obtained by packing 0.47 g of asample into a molding machine having a diameter of 17 mm and compactingthe sample at 58.8 MN·m⁻² is set with clay on a sample holder forexamination so as to be flush with the holder. This sample is examinedfor X-ray diffraction. From the intensities of the resultant (110)diffraction peak and (004) diffraction peak for the carbon, the ratiorepresented by (110) diffraction peak intensity/(004) diffraction peakintensity is calculated. The orientation ratio calculated through thismeasurement is defined as the orientation ratio of the carbonaceousmaterial according to the invention.

Conditions for the X-ray diffractometry are as follows. Incidentally,“20” represents diffraction angle.

Target: Cu (Kα line) graphite monochromator

Slits:

Divergence slit=0.5 degrees

Receiving slit=0.15 mm

Scattering slit=0.5 degrees

Examination range and step angle/measuring time:

(110) plane: 75° ≦ 2θ ≦ 80° 1°/60 sec (004) plane: 52° ≦ 2θ ≦ 57° 1°/60sec(8) Aspect Ratio (Powder)

The aspect ratio of the carbonaceous material is generally 1 or greater,and is generally 10 or less, preferably 8 or less, more preferably 5 orless. When the aspect ratio thereof exceeds that range, there are caseswhere the carbonaceous material causes streak lines in electrode plateformation and an even coating surface cannot be obtained, resulting in adecrease in high-current-density charge/discharge characteristics.Incidentally, the lower limit of that range is a theoretical lower limitof the aspect ratio of carbonaceous materials.

In determining aspect ratio, particles of the carbonaceous material areexamined with a scanning electron microscope with enlargement. Fifty arearbitrarily selected from graphite particles fixed to an edge face of ametal having a thickness of 50 μm or less, and each particle is examinedin a three-dimensional manner while rotating and inclining the stage towhich the sample is fixed. In this examination, the length of thelongest axis A of each carbonaceous-material particle and the length ofthe shortest axis B perpendicular to that axis are measured, and theaverage of the A/B values is determined. The aspect ratio (A/B)determined through this measurement is defined as the aspect ratio ofthe carbonaceous material according to the invention.

(9) Electrode Production

Any known method can be used for electrode production unless thisconsiderably lessens the effects of the invention. For example, a binderand a solvent are added to a negative-electrode active materialoptionally together with a thickener, conductive material, filler, etc.to obtain a slurry, and this slurry is applied to a current collectorand dried. Thereafter, the coated current collector is pressed. Thus, anelectrode can be formed.

At the stage just before the step of introducing the nonaqueouselectrolytic solution in battery production, the thickness of thenegative-electrode active-material layer per surface is generally 15 μmor more, preferably 20 μm or more, more preferably 30 μm or more, and isgenerally 150 μm or less, preferably 120 μm or less, more preferably 100μm or less. The reasons for this are as follows. When the thickness ofthe negative-electrode active material exceeds that range, there arecases where high-current-density charge/discharge characteristicsdecrease because the nonaqueous electrolytic solution is less apt toinfiltrate into around the current collector interface. Furthermore,when the thickness thereof is less than that range, there are caseswhere the battery has a reduced capacity because the volume ratio of thecurrent collector to the negative-electrode active material is high.Meanwhile, a negative-electrode active material may be formed into asheet electrode by rolling, or may be compression-molded into a pelletelectrode.

(10) Current Collector

As the current collector for holding the negative-electrode activematerial, a known current collector can be used at will. Examples of thecurrent collector for the negative electrode include metallic materialssuch as copper, nickel, stainless steel, and nickel-plated steel. Copperis especially preferred from the standpoints of processability and cost.

In the case where the current collector is a metallic material, examplesof the shape of the current collector include metal foils, metalcylinders, metal coils, metal plates, thin metal films, expanded metals,punching metals, and metal foam. Preferred of these are thin metalfilms. More preferred are copper foils. Even more preferred are a rolledcopper foil, which is produced by the rolling process, and anelectrolytic copper foil, which is produced by the electrolytic process.Either of these can be used as a current collector.

In the case where a copper foil having a thickness less than 25 μm is tobe used, this copper foil can be a foil of a copper alloy (phosphorbronze, titanium-copper, Corson alloy, Cu—Cr—Zr alloy, etc.) which hashigher strength than pure copper.

(10-1) Thickness of Current Collector

The current collector may have any desired thickness. However, thethickness thereof is generally 1 μm or more, preferably 3 μm or more,more preferably 5 μm or more, and is generally 1 mm or less, preferably100 μm or less, more preferably 50 μm or less. When the thickness of themetal film is less than 1 μm, there are cases where coating fluidapplication thereto is difficult because of the reduced strengththereof. When the thickness thereof is larger than 100 μm, there arecases where the electrode shape obtained by, for example, winding isdeformed. Incidentally, the current collector may be a meshy material.

(11) Thickness Ratio Between Current Collector and Negative-ElectrodeActive-Material Layer

The thickness ratio between the current collector and thenegative-electrode active-material layer is not particularly limited.However, the value of “(thickness of the negative-electrodeactive-material layer on one surface just before impregnation withnonaqueous electrolytic solution)/(thickness of the current collector)”is preferably 150 or less, more preferably 20 or less, especiallypreferably 10 or less, and is preferably 0.1 or greater, more preferably0.4 or greater, especially preferably 1 or greater.

When the thickness ratio between the current collector and thenegative-electrode active-material layer exceeds that range, there arecases where this current collector is heated up by Joule's heat duringhigh-current-density charge/discharge. When the thickness ratiotherebetween is less than that range, there are cases where the batteryhas a reduced capacity because the proportion by volume of the currentcollector to the negative-electrode active material is high.

(12) Electrode Density

The structure of the electrode formed using a negative-electrode activematerial is not particularly limited. However, the density of thenegative-electrode active material present on the current collector ispreferably 1 g·cm⁻³ or higher, more preferably 1.2 g·cm⁻³ or higher,especially preferably 1.3 g·cm⁻³ or higher, and is preferably 2.2 g·cm⁻³or less, more preferably 2.1 g·cm⁻³ or less, even more preferably 2.0g·cm⁻³ or less, especially preferably 1.9 g·cm⁻³ or less. When thedensity of the negative-electrode active material present on the currentcollector exceeds that range, there are cases where thenegative-electrode active-material particles are broken and thisincreases the initial irreversible capacity and reduces the infiltrationof the nonaqueous electrolytic solution into around the currentcollector/negative-electrode active material interface, resulting in adeterioration in high-current-density charge/discharge characteristics.When the density thereof is less than that range, there are cases whereelectrical conductivity among the negative-electrode active-materialparticles decreases and this increases battery resistance, resulting ina decrease in capacity per unit volume.

(13) Binder

The binder for binding the negative-electrode active material is notparticularly limited so long as the binder is stable to the nonaqueouselectrolytic solution and to the solvent to be used for electrodeproduction.

Examples thereof include resinous polymers such as polyethylene,polypropylene, poly(ethylene terephthalate), poly(methyl methacrylate),aromatic polyamides, cellulose, and nitrocellulose; rubbery polymerssuch as SBR (styrene/butadiene rubbers), isoprene rubbers, butadienerubbers, fluororubbers, NBR (acrylonitrile/butadiene rubbers), andethylene/propylene rubbers; styrene/butadiene/styrene block copolymersor products of hydrogenation thereof; thermoplastic elastomeric polymerssuch as EPDM (ethylene/propylene/diene terpolymers),styrene/ethylene/butadiene/styrene copolymers, andstyrene/isoprene/styrene block copolymers or products of hydrogenationthereof; flexible resinous polymers such as syndiotactic1,2-polybutadiene, poly(vinyl acetate), ethylene/vinyl acetatecopolymers, and propylene/α-olefin copolymers; fluorochemical polymerssuch as poly(vinylidene fluoride), polytetrafluoroethylene, fluorinatedpoly(vinylidene fluoride), and polytetrafluoroethylene/ethylenecopolymers; and polymer compositions having the property of conductingalkali metal ions (especially lithium ions). One of these binders may beused alone, or any desired two or more thereof may be used incombination in any desired proportion.

The kind of the solvent to be used for forming a slurry is notparticularly limited so long as the negative-electrode active materialand binder and the thickener and conductive material which areoptionally used according to need can be dissolved or dispersed therein.Either an aqueous solvent or an organic solvent may be used.

Examples of the aqueous solvent include water and alcohols. Examples ofthe organic solvent include N-methylpyrrolidone (NMP),dimethylformamide, dimethylacetamide, methyl ethyl ketone,cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine,N,N-dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone,diethyl ether, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, andhexane.

Especially when an aqueous solvent is used, it is preferred to add adispersant or the like in combination with a thickener and prepare aslurry using a latex of, for example, SBR. One of those solvents may beused alone, or any desired two or more thereof may be used incombination in any desired proportion.

The proportion of the binder to the negative-electrode active materialis preferably 0.1% by mass or higher, more preferably 0.5% by mass orhigher, especially preferably 0.6% by mass or higher, and is preferably20% by mass or less, more preferably 15% by mass or less, even morepreferably 10% by mass or less, especially preferably 8% by mass orless. When the proportion of the binder to the negative-electrode activematerial exceeds that range, there are cases where the proportion of thebinder which does not contribute to battery capacity increases and thisleads to a decrease in battery capacity. When the proportion thereof isless than that range, there are cases where the negative electrode has areduced strength.

Especially when the binder includes a rubbery polymer represented by SBRas the main component, the proportion of this binder to thenegative-electrode active material is generally 0.1% by mass or higher,preferably 0.5% by mass or higher, more preferably 0.6% by mass orhigher, and is generally 5% by mass or less, preferably 3% by mass orless, more preferably 2% by mass or less.

In the case where the binder includes a fluorochemical polymerrepresented by poly(vinylidene fluoride) as the main component, theproportion of this binder to the negative-electrode active material isgenerally 1% by mass or higher, preferably 2% by mass or higher, morepreferably 3% by mass or higher, and is generally 15% by mass or less,preferably 10% by mass or less, more preferably 8% by mass or less.

A thickener is used generally for the purpose of regulating the slurryviscosity. The thickener is not particularly limited. Examples thereofinclude carboxymethyl cellulose, methyl cellulose, hydroxymethylcellulose, ethyl cellulose, poly(vinyl alcohol), oxidized starch,phosphorylated starch, casein, and salts of these. One of thesethickeners may be used alone, or any desired two or more thereof may beused in combination in any desired proportion.

In the case where such a thickener is further added, the proportion ofthe thickener to the negative-electrode active material is generally0.1% by mass or higher, preferably 0.5% by mass or higher, morepreferably 0.6% by mass or higher, and is generally 5% by mass or less,preferably 3% by mass or less, more preferably 2% by mass or less. Whenthe proportion of the thickener to the negative-electrode activematerial is less than that range, there are cases where applicabilitydecreases considerably. When the proportion thereof exceeds that range,the proportion of the negative-electrode active material in thenegative-electrode active-material layer is low. There is hence aproblem that the battery has a reduced capacity, and there are caseswhere resistance among the particles of the negative-electrode activematerial increases.

<2-3-3. Metal Compound Material, Configuration and Properties ofNegative Electrode Employing Metal Compound Material, and Methods forPreparing the Negative Electrode>

The metal compound material to be used as a negative-electrode activematerial is not particularly limited so long as the material is capableof occluding and releasing lithium. The metal compound material may bean elemental metal or alloy which forms a lithium alloy or may be any ofcompounds of such metals, such as oxides, carbides, nitrides, silicides,sulfides, and phosphides. Examples of such metal compounds includecompounds containing metals such as Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni,P, Pb, Sb, Si, Sn, Sr, and Zn. Preferred of these is an elemental metalor alloy which forms a lithium alloy. More preferred is a material whichincludes a metallic or semimetallic element belonging to Group 13 orGroup 14 (that is, carbon is excluded). Even more preferred is theelemental metal of silicon (Si), tin (Sn), or lead (Pb) (hereinafter,these three elements are often referred to as “specific metallicelements”), an alloy which contains one or more atoms of these elements,or a compound of any of these metals (specific metallic elements).Especially preferred are the elemental metal, alloys, and compounds ofsilicon and the elemental metal, alloys, and compounds of tin. One ofthese materials may be used alone, or any desired two or more thereofmay be used in combination in any desired proportion.

Examples of the negative-electrode active material which has atoms of atleast one member selected from the specific metallic elements include:the elemental metal which is any one of the specific metallic elements;alloys constituted of two or more specific metallic elements; alloysconstituted of one or more specific metallic elements and one or moreother metallic elements; and compounds containing one or more specificmetallic elements or composite compounds, e.g., oxides, carbides,nitrides, silicides, sulfides, and phosphides, of these compounds. Byusing any of these elemental metals, alloys, and metal compounds as anegative-electrode active material, a battery having a higher capacitycan be obtained.

Examples of the negative-electrode active material further includecompounds formed by the complicated bonding of any of those compositecompounds to one or more elemental metals or alloys or to severalelements, e.g., nonmetallic elements. Specifically, in the case ofsilicon and tin, for example, use can be made of an alloy of thoseelements with a metal which does not function as a negative electrode.In the case of tin, for example, use can be made of a complicatedcompound constituted of a combination of five to six elements includingtin, a metal which functions as a negative electrode and is not silicon,a metal which does not function as a negative electrode, and anonmetallic element.

Preferred of those negative-electrode active materials are the elementalmetal which is any one of the specific metallic elements, alloys of twoor more of the specific metallic elements, and oxides, carbides,nitrides, and other compounds of the specific metallic elements. This isbecause these negative-electrode active materials give a battery havinga high capacity per unit mass. Especially preferred are the elementalmetal(s), alloys, oxides, carbides, nitrides, and the like of siliconand/or tin from the standpoints of capacity per unit mass andenvironmental burden.

The following compounds containing silicon and/or tin are also preferredbecause these compounds bring about excellent cycle characteristicsalthough inferior in capacity per unit mass to the metallic elements oralloys.

An “oxide of silicon and/or tin” in which the element ratio of siliconand/or tin to oxygen is generally 0.5 or greater, preferably 0.7 orgreater, more preferably 0.9 or greater, and is generally 1.5 or less,preferably 1.3 or less, more preferably 1.1 or less.

A “nitride of silicon and/or tin” in which the element ratio of siliconand/or tin to nitrogen is generally 0.5 or greater, preferably 0.7 orgreater, more preferably 0.9 or greater, and is generally 1.5 or less,preferably 1.3 or less, more preferably 1.1 or less.

A “carbide of silicon and/or tin” in which the element ratio of siliconand/or tin to carbon is generally 0.5 or greater, preferably 0.7 orgreater, more preferably 0.9 or greater, and is generally 1.5 or less,preferably 1.3 or less, more preferably 1.1 or less.

Any one of the negative-electrode active materials described above maybe used alone, or any desired two or more thereof may be used incombination in any desired proportion.

The negative electrode in the nonaqueous-electrolyte secondary batteryof the invention can be produced using any of known methods. Examples ofmethods for producing the negative electrode include: a method in whicha mixture obtained by adding a binder, a conductive material, etc. toany of the negative-electrode active materials described above is formedas such into a sheet electrode by rolling; and a method in which themixture is compression-molded into a pellet electrode. Usually, however,use is made of a method in which a thin-film layer (negative-electrodeactive-material layer) that contains any of the negative-electrodeactive materials described above is formed on a current collector fornegative electrodes (hereinafter often referred to as“negative-electrode current collector”) by a technique such as coatingfluid application, vapor deposition, sputtering, or plating. In thiscase, a binder, thickener, conductive material, solvent, etc. are addedto the negative-electrode active material to obtain a slurry and thisslurry is applied to a negative-electrode current collector and dried.Thereafter, the coated negative-electrode current collector is pressedto densify the coating film, thereby forming a negative-electrodeactive-material layer on the negative-electrode current collector.

Examples of the material of the negative-electrode current collectorinclude steel, copper alloys, nickel, nickel alloys, and stainlesssteel. Preferred of these are copper foils from the standpoints of easeof processing into thin films and cost.

The thickness of the negative-electrode current collector is generally 1μm or more, preferably 5 μm or more, and is generally 100 μm or less,preferably 50 μm or less. The reasons for this are as follows. When thenegative-electrode current collector has too large a thickness, thereare cases where the battery as a whole has an excessively reducedcapacity. Conversely, too small thicknesses thereof render the currentcollector difficult to handle.

It is preferred that the surfaces of the negative-electrode currentcollector should be subjected to a surface-roughening treatmentbeforehand in order to improve the effect of binding to thenegative-electrode active-material layer to be formed on the surfaces.Examples of techniques for the surface roughening include blasting,rolling with a roll having a roughened surface, a mechanical polishingmethod in which the current collector surfaces are polished with apolishing cloth or paper having abrasive grains fixed thereto or with agrindstone, emery buff, wire brush equipped with steel bristles, etc.,an electrolytic polishing method, and a chemical polishing method.

For the purpose of reducing the mass of a negative-electrode currentcollector to improve the energy density of the battery per unit mass,use can be made of a negative-electrode current collector of aperforated type, such as an expanded metal or a punching metal. Thistype of negative-electrode current collector can be freely changed inmass by changing the percentage of openings thereof. Furthermore, in thecase where a negative-electrode active-material layer has been formed oneach of both surfaces of this type of negative-electrode currentcollector, the negative-electrode active-material layers are even lessapt to peel off because of the rivet effect due to the holes. However,in case where the negative-electrode current collector has too high apercentage of openings, the area of contact between thenegative-electrode active-material layer and the negative-electrodecurrent collector is reduced. There are hence cases where the adhesionstrength decreases rather than increases.

The slurry for forming a negative-electrode active-material layer isproduced usually by adding a binder, a thickener, etc. to anegative-electrode material. The term “negative-electrode material” inthis description means a material which includes both anegative-electrode active material and a conductive material.

It is preferred that the content of the negative-electrode activematerial in the negative-electrode material should be generally 70% bymass or higher, especially 75% by mass or higher, and be generally 97%by mass or less, especially 95% by mass or less. The reasons for thisare as follows. In case where the content of the negative-electrodeactive material is too low, the secondary battery employing the negativeelectrode thus obtained tends to have an insufficient capacity. In casewhere the content thereof is too high, the content of the binder andother components is relatively insufficient and, hence, the negativeelectrode obtained tends to have insufficient strength. Incidentally, inthe case where two or more negative-electrode active materials are usedin combination, these negative-electrode active materials may beincorporated so that the total amount thereof satisfies that range.

Examples of the conductive material for use in the negative electrodeinclude metallic materials such as copper and nickel and carbonmaterials such as graphite and carbon black. One of such materials maybe used alone, or any desired two or more thereof may be used incombination in any desired proportion. In particular, use of a carbonmaterial as the conductive material is preferred because the carbonmaterial functions also as an active material. It is preferred that thecontent of the conductive material in the negative-electrode materialshould be generally 3% by mass or higher, especially 5% by mass orhigher, and be generally 30% by mass or less, especially 25% by mass orless. The reasons for this are as follows. In case where the content ofthe conductive material is too low, the resultant negative electrodetends to have insufficient electrical conductivity. In case where thecontent thereof is too high, the content of the negative-electrodeactive material and other components is relatively insufficient and,hence, battery capacity and strength tend to decrease. Incidentally, inthe case where two or more conductive materials are used in combination,these conductive materials may be incorporated so that the total amountthereof satisfies that range.

As the binder for the negative electrode, use can be made of any desiredmaterial which is safe for the solvent and electrolytic solution to beused in electrode production. Examples thereof include poly(vinylidenefluoride), polytetrafluoroethylene, polyethylene, polypropylene,styrene/butadiene rubbers, isoprene rubbers, butadiene rubbers,ethylene/acrylic acid copolymers, and ethylene/methacrylic acidcopolymers. One of these materials may be used alone, or any desired twoor more thereof may be used in combination in any desired proportion. Itis preferred that the content of the binder per 100 parts by mass of thenegative-electrode material should be generally 0.5 parts by mass ormore, especially 1 part by mass or more, and be generally 10 parts bymass or less, especially 8 parts by mass or less. The reasons for thisare follows. In case where the content of the binder is too low, thenegative electrode obtained tends to have insufficient strength. In casewhere the content thereof is too high, the content of thenegative-electrode active material and other components is relativelyinsufficient and, hence, battery capacity and electrical conductivitytend to become insufficient. Incidentally, in the case where two or morebinders are used in combination, these binders may be incorporated sothat the total amount thereof satisfies that range.

Examples of the thickener to be used for the negative electrode includecarboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose,ethyl cellulose, poly(vinyl alcohol), oxidized starch, phosphorylatedstarch, and casein. One of these thickeners may be used alone, or anydesired two or more thereof may be used in combination in any desiredproportion. A thickener may be used according to need. In the case ofusing a thickener, however, it is preferred to use the thickener so thatthe content of the thickener in the negative-electrode active-materiallayer is generally in the range of 0.5-5% by mass.

The slurry for forming a negative-electrode active-material layer isprepared by mixing the negative-electrode active material with aconductive material, a binder, and a thickener according to need usingan aqueous solvent or an organic solvent as a dispersion medium. Wateris usually used as the aqueous medium. However, a solvent other thanwater, such as, for example, an alcohol, e.g., ethanol, or a cyclicamide, e.g., N-methylpyrrolidone, can be used in combination with waterin an amount of up to about 30% by mass based on the water. Preferredorganic solvents usually include aromatic amides such asN-methylpyrrolidone, linear amides such as N,N-dimethylformamide andN,N-dimethylacetamide, aromatic hydrocarbons such as anisole, toluene,and xylene, and alcohols such as butanol and cyclohexanol. Preferred ofthese are cyclic amides such as N-methylpyrrolidone and linear amidessuch as N,N-dimethylformamide and N,N-dimethylacetamide. Any one ofthese solvents may be used alone, or any desired two or more thereof maybe used in combination in any desired proportion.

The viscosity of the slurry is not particularly limited so long as theviscosity thereof renders the slurry applicable to the currentcollector. The slurry may be suitably prepared so as to attain suchviscosity which renders the slurry applicable, by changing the amount ofthe solvent to be use for the slurry preparation.

The slurry obtained is applied to the negative-electrode currentcollector described above, subsequently dried, and then pressed. Thus, anegative-electrode active-material layer is formed. Techniques for theapplication are not particularly limited, and use can be made of atechnique which itself is known. Techniques for the drying also are notparticularly limited, and use can be made of a known technique such asair drying, drying by heating, or vacuum drying.

The structure of the electrode formed using a negative-electrode activematerial by the method described above is not particularly limited.However, the density of the active material present on the currentcollector is preferably 1 g·cm⁻³ or higher, more preferably 1.2 g·cm⁻³or higher, especially preferably 1.3 g·cm⁻³ or higher, and is preferably2.2 g·cm⁻³ or less, more preferably 2.1 g·cm⁻³ or less, even morepreferably 2.0 g·cm⁻³ or less, especially preferably 1.9 g·cm⁻³ or less.

When the density of the active material present on the current collectorexceeds that range, there are cases where the active-material particlesare broken and this increases the initial irreversible capacity andreduces the infiltration of the nonaqueous electrolytic solution intoaround the current collector/active material interface, resulting in adeterioration in high-current-density charge/discharge characteristics.When the density thereof is less than that range, there are cases whereelectrical conductivity among the active-material particles decreasesand this increases battery resistance, resulting in a decrease incapacity per unit volume.

<2-3-4. Lithium-Containing Composite Metal Oxide Material, Configurationand Properties of Negative Electrode Employing Lithium-ContainingComposite Metal Oxide Material, and Methods for Preparing the NegativeElectrode>

The lithium-containing composite metal oxide material to be used as anegative-electrode active material is not particularly limited so longas the material is capable of occluding and releasing lithium. However,lithium-containing composite metal oxide materials which containtitanium are preferred, and a composite oxide of lithium and titanium(hereinafter often referred to simply as “lithium-titanium compositeoxide”) is especially preferred. Namely, a lithium-titanium compositeoxide having a spinel structure is especially preferred because use of anegative-electrode active material for nonaqueous-electrolyte secondarybatteries which includes that composite oxide brings about a significantdecrease in output resistance.

Also preferred is a lithium-titanium composite oxide in which thelithium and the titanium have been replaced with one or more othermetallic elements, e.g., at least one element selected from the groupconsisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.

It is preferred that the metal oxide should be a lithium-titaniumcomposite oxide represented by general formula (5) wherein 0.7≦x≦1.5,1.5≦y≦2.3, and 0≦z≦1.6, because this composite oxide retains a stablestructure during lithium-ion doping/undoping.Li_(x)Ti_(y)M_(z)O₄  (5)[In general formula (5), M represents at least one element selected fromthe group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, andNb.]

Especially preferred of the compositions represented by general formula(5) are the following structures.

(a) 1.2≦x≦1.4, 1.5≦y≦1.7, z=0

(b) 0.9≦x≦1.1, 1.9≦y≦2.1, z=0

(c) 0.7≦x≦0.9, 2.1≦y≦2.3, z=0

This is because these structures bring about a satisfactory balanceamong battery performances.

Especially preferred representative compositions of that compound areLi_(4/3)Ti_(5/3)O₄ for (a), Li₁Ti₂O₄ for (b), andLi_(4/5)Ti_(4/5)Al_(11/5)O₄ for (c). With respect to structures in whichZ≠0, preferred examples thereof include L_(4/3)Ti_(4/3)Al_(1/3)O₄.

It is preferred that the lithium-titanium composite oxide to be used asa negative-electrode active material in the invention should satisfy atleast one of the following features (1) to (13) concerning properties,shape, etc., besides the requirements shown above. It is especiallypreferred that the composite oxide should simultaneously satisfy two ormore of the following features.

(1) BET Specific Surface Area

The BET specific surface area of the lithium-titanium composite oxide tobe used as a negative-electrode active material, in terms of the valueof specific surface area as determined by the BET method, is preferably0.5 m²·g⁻¹ or larger, more preferably 0.7 m²·g⁻¹ or larger, even morepreferably 1.0 m²·g⁻¹ or larger, especially preferably 1.5 m²·g⁻¹ orlarger, and is preferably 200 m²·g⁻¹ or less, more preferably 100 m²·g⁻¹or less, even more preferably 50 m²·g⁻¹ or less, especially preferably25 m²·g⁻¹ or less.

When the BET specific surface area thereof is less than that range, thiscomposite oxide, when used as a negative-electrode material, has areduced reaction area where the composite oxide is in contact with thenonaqueous electrolytic solution. There are hence cases where the outputresistance increases. On the other hand, in case where the BET specificsurface area thereof exceeds that range, the proportion of the surfacesand the edge faces in the crystals of the titanium-containing metaloxide increases and crystal strains occur due to this increase.Consequently, there are cases where irreversible capacity becomes notnegligible and a preferred battery is difficult to obtain.

The determination of specific surface area by the BET method is madewith a surface area meter (a fully automatic surface area measuringapparatus manufactured by Ohkura Riken Co., Ltd.) by preliminarilydrying a sample at 350° C. for 15 minutes in a nitrogen stream and thenmeasuring the specific surface area thereof by the gas-flowing nitrogenadsorption BET one-point method using a nitrogen/helium mixture gasprecisely regulated so as to have a nitrogen pressure of 0.3 relative toatmospheric pressure. The specific surface area determined through thismeasurement is defined as the BET specific surface area of thelithium-titanium composite oxide according to the invention.

(2) Volume-Average Particle Diameter

The volume-average particle diameter of the lithium-titanium compositeoxide (in the case where the primary particles have aggregated to formsecondary particles, that volume-average particle diameter is thediameter of the secondary particles) is defined as a volume-averageparticle diameter (median diameter) as determined by the laserdiffraction/scattering method.

The volume-average particle diameter of the lithium-titanium compositeoxide is generally 0.1 μm or more, preferably 0.5 μm or more, morepreferably 0.7 μm or more, and is generally 50 μm or less, preferably 40μm or less, even more preferably 30 μm or less, especially preferably 25μm or less.

Volume-average particle diameter is determined by dispersing the carbonpowder in a 0.2% by mass aqueous solution (10 mL) ofpoly(oxyethylene(20)) sorbitan monolaurate as a surfactant and examiningthe dispersion with a laser diffraction/scattering type particle sizedistribution analyzer (LA-700, manufactured by HORIBA, Ltd.). The mediandiameter determined through this measurement is defined as thevolume-average particle diameter of the carbonaceous material accordingto the invention.

In case where the volume-average particle diameter of thelithium-titanium composite oxide is less than that range, a large amountof a binder is necessary for electrode production and there are caseswhere the large binder amount results in a decrease in battery capacity.When the volume-average particle diameter thereof exceeds that range,there are cases where such a composite oxide is undesirable from thestandpoint of battery production because an uneven coating surface isapt to result during electrode plate formation.

(3) Average Primary-Particle Diameter

In the case where the primary particles have aggregated to formsecondary particles, the average primary-particle diameter of thelithium-titanium composite oxide is generally 0.01 μm or more,preferably 0.05 μm or more, more preferably 0.1 μm or more, especiallypreferably 0.2 μm or more, and is generally 2 μm or less, preferably 1.6μm or less, more preferably 1.3 μm or less, especially preferably 1 μmor less. In case where the volume-average primary-particle diameterthereof exceeds that range, such primary particles are less apt to formspherical secondary particles, resulting in an adverse influence onpowder loading, and this material has a considerably reduced specificsurface area. There are hence cases where battery performances, e.g.,output characteristics, are apt to decrease. When the averageprimary-particle diameter thereof is less than that range, the crystalsusually are in an insufficiently grown state and, hence, there are caseswhere this composite oxide makes the secondary battery have reducedperformances, e.g., poor charge/discharge reversibility.

Incidentally, primary-particle diameter is determined through anexamination with a scanning electron microscope (SEM). Specifically,arbitrarily selected 50 primary-particle images in a photograph having amagnification which renders the particles recognizable, e.g.,10,000-100,000 diameters, each are examined for the length of thelongest segment of a horizontal line which extends across theprimary-particle image from one side to the other side of the boundary.These measured lengths are averaged to determine the average value.

(4) Shape

The shape of the particles of the lithium-titanium composite oxide maybe any of massive, polyhedral, spherical, ellipsoidal, platy, acicular,columnar, and other shapes such as those in common use. Preferred ofthese is one in which the primary particles have aggregated to formsecondary particles and these secondary particles have a spherical orellipsoidal shape.

In electrochemical elements, the active material in each electrodeusually expands/contracts with the charge/discharge of the element and,hence, a deterioration, such as active-material breakage or conductionpath breakage, that is caused by the resultant stress is apt to occur.Consequently, an active material in which the primary particles haveaggregated to form secondary particles is preferable to an activematerial composed of primary particles only, since the particles in theformer active material relieve the stress caused byexpansion/contraction to prevent the deterioration.

Furthermore, particles of a spherical or ellipsoidal shape arepreferable to particles showing axial orientation, e.g., platyparticles, because the former particles are less apt to orient duringelectrode forming and hence this electrode is reduced inexpansion/contraction during charge/discharge, and because theseparticles are apt to be evenly mixed with a conductive material inelectrode production.

(5) Tap Density

The tap density of the lithium-titanium composite oxide is preferably0.05 g·cm⁻³ or higher, more preferably 0.1 g·cm⁻³ or higher, even morepreferably 0.2 g·cm⁻³ or higher, especially preferably 0.4 g·cm⁻³ orhigher, and is preferably 2.8 g·cm⁻³ or less, more preferably 2.4 g·cm⁻³or less, especially preferably 2 g·cm⁻³ or less. In case where the tapdensity thereof is less than that range, this composite oxide, when usedin a negative electrode, is less apt to attain an increased loadingdensity and has a reduced area of contact between the particles. Thereare hence cases where interparticle resistance increases and outputresistance increases. In case where the tap density thereof exceeds thatrange, the amount of interparticle interstices in the electrode becomestoo small and the amount of passages for the nonaqueous electrolyticsolution decreases. There are hence cases where output resistanceincreases.

Tap density is determined by dropping a sample through a sieve having anopening size of 300 μm into a 20-cm³ tapping cell to fill the cell withthe sample up to the brim, subsequently conducting a tapping operation1,000 times over a stroke length of 10 mm using a powder densimeter(e.g., Tap Denser, manufactured by Seishin Enterprise Co., Ltd.), andcalculating the density from the resultant volume of the sample and themass thereof. The tap density calculated through this measurement isdefined as the tap density of the lithium-titanium composite oxideaccording to the invention.

(6) Roundness

When the lithium-titanium composite oxide is examined for roundness asan index to the degree of sphericity thereof, the roundness thereof ispreferably within the range shown below. Roundness is defined by“Roundness=(length of periphery of equivalent circle having the samearea as projected particle shape)/(actual length of periphery ofprojected particle shape)”. When a particle has a roundness of 1, thisparticle theoretically is a true sphere.

The closer to 1 the roundness of the lithium-titanium composite oxide,the more the composite oxide is preferred. The roundness of thecomposite oxide is generally 0.10 or higher, preferably 0.80 or higher,more preferably 0.85 or higher, especially preferably 0.90 or higher.The higher the roundness, the more the high-current-densitycharge/discharge characteristics are improved. Consequently, in casewhere the roundness thereof is less than that range, thenegative-electrode active material has reduced loading characteristicsand enhanced interparticle resistance. There are hence cases whereshort-time high-current-density charge/discharge characteristicsdecrease.

Roundness is determined with a flow type particle image analyzer (FPIA,manufactured by Sysmex Industrial Corp.). About 0.2 g of a sample isdispersed in a 0.2% by mass aqueous solution (about 50 mL) ofpoly(oxyethylene(20)) sorbitan monolaurate as a surfactant, and anultrasonic wave of 28 kHz is propagated to the dispersion for 1 minuteat an output of 60 W. Thereafter, particles having a particle diameterin the range of 3-40 μm are examined with the analyzer having adetection range set at 0.6-400 μm. The roundness determined through thismeasurement is defined as the roundness of the lithium-titaniumcomposite oxide according to the invention.

(7) Aspect Ratio

The aspect ratio of the lithium-titanium composite oxide is generally 1or greater, and is generally 5 or less, preferably 4 or less, morepreferably 3 or less, especially preferably 2 or less. When the aspectratio thereof exceeds that range, there are cases where the compositeoxide causes streak lines in electrode plate formation and an evencoating surface cannot be obtained, resulting in a decrease inshort-time high-current-density charge/discharge characteristics.Incidentally, the lower limit of that range is a theoretical lower limitof the aspect ratio of the lithium-titanium composite oxide.

In determining aspect ratio, particles of the lithium-titanium compositeoxide are examined with a scanning electron microscope with enlargement.Fifty are arbitrarily selected from particles fixed to an edge face of ametal having a thickness of 50 μm or smaller, and each particle isexamined in a three-dimensional manner while rotating and inclining thestage to which the sample is fixed. In this examination, the length ofthe longest axis A of each particle and the length of the shortest axisB perpendicular to that axis are measured, and the average of the A/Bvalues is determined. The aspect ratio (A/B) determined through thismeasurement is defined as the aspect ratio of the lithium-titaniumcomposite oxide according to the invention.

(8) Processes for Producing the Negative-Electrode Active Material

Processes for producing the lithium-titanium composite oxide are notparticularly limited unless the processes depart from the spirit of theinvention. Examples thereof include several processes, and use may bemade of general processes for producing inorganic compounds.

Examples thereof include a process in which a titanium source, e.g.,titanium oxide, is evenly mixed optionally with a source of anotherelement and with a lithium source, e.g., LiOH, Li₂CO₃, or LiNO₃, and themixture is burned at a high temperature to obtain an active material.

Various processes are thought to be usable for producing, in particular,a spherical or ellipsoidal active material. Examples thereof include aprocess in which a titanium source, e.g., titanium oxide, and a sourceof another element, which is used according to need, are dissolved in orpulverized and dispersed in a solvent, e.g., water, and the pH of thissolution or dispersion is regulated with stirring to produce sphericalprecursor particles. The precursor particles are recovered andoptionally dried. A lithium source, e.g., LiOH, Li₂CO₃, or LiNO₃, isadded to the precursor, and the mixture is burned at a high temperatureto obtain an active material.

Another example is a process in which a titanium source, e.g., titaniumoxide, and a source of another element, which is used according to need,are dissolved in or pulverized and dispersed in a solvent, e.g., water,and this solution or dispersion is dried and molded with a spray dryeror the like to obtain spherical or ellipsoidal precursor particles. Alithium source, e.g., LiOH, Li₂CO₃, or LiNO₃, is added to the precursor,and the mixture is burned at a high temperature to obtain an activematerial.

Still another process is a process in which a titanium source, e.g.,titanium oxide, a lithium source, e.g., LiOH, Li₂CO₃, or LiNO₃, and asource of another element, which is used according to need, aredissolved in or pulverized and dispersed in a solvent, e.g., water, andthis solution or dispersion is dried and molded with a spray dryer orthe like to obtain spherical or ellipsoidal precursor particles. Thisprecursor is burned at a high temperature to obtain an active material.

During these steps, elements other than Ti, such as, for example, Al,Mn, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, C, Si, Sn, andAg, can be present so that these elements are present in the structureof the titanium-containing metal oxide and/or are in contact with thetitanium-containing oxide. Use of the lithium-titanium composite oxidewhich contains these elements makes it possible to regulate theoperating voltage and capacity of the battery.

(9) Electrode Production

Any known method can be used for electrode production. For example, abinder and a solvent are added to a negative-electrode active materialoptionally together with a thickener, conductive material, filler, etc.to obtain a slurry and this slurry is applied to a current collector anddried. Thereafter, the coated current collector is pressed. Thus, anelectrode can be formed.

At the stage just before the step of introducing the nonaqueouselectrolytic solution in battery production, the thickness of thenegative-electrode active-material layer per surface is generally 15 μmor more, preferably 20 μm or more, more preferably 30 μm or more. It isdesirable that the upper limit thereof should be 150 μm or less,preferably 120 μm or less, more preferably 100 μm or less.

When the thickness of the negative-electrode active-material layerexceeds that range, there are cases where high-current-densitycharge/discharge characteristics decrease because the nonaqueouselectrolytic solution is less apt to infiltrate into around the currentcollector interface. Furthermore, when the thickness thereof is lessthan that range, there are cases where the battery has a reducedcapacity because the volume ratio of the current collector to thenegative-electrode active material is high. Meanwhile, anegative-electrode active material may be formed into a sheet electrodeby rolling, or may be compression-molded into a pellet electrode.

(10) Current Collector

As the current collector for holding the negative-electrode activematerial, a known current collector can be used at will. Examples of thecurrent collector for the negative electrode include metallic materialssuch as copper, nickel, stainless steel, and nickel-plated steel. Copperis especially preferred of these from the standpoints of processabilityand cost.

In the case where the current collector is a metallic material, examplesof the shape of the current collector include metal foils, metalcylinders, metal coils, metal plates, thin metal films, expanded metals,punching metals, and metal foam. Preferred of these are metal foilswhich contain copper (Cu) and/or aluminum (Al). More preferred arecopper foils and aluminum foils. Even more preferred are a rolled copperfoil, which is produced by the rolling process, and an electrolyticcopper foil, which is produced by the electrolytic process. Either ofthese can be used as a current collector.

In the case where a copper foil having a thickness less than 25 μm is tobe used, this copper foil can be a foil of a copper alloy (phosphorbronze, titanium-copper, Corson alloy, Cu—Cr—Zr alloy, etc.) which hashigher strength than pure copper. Use of an aluminum foil as a currentcollector is preferred because aluminum has a small specific gravity andit is hence possible to reduce the mass of the battery.

A current collector constituted of a copper foil produced by the rollingprocess is suitable for use in small cylindrical batteries because thecopper crystals have been oriented along the rolling direction and,hence, this current collector is less apt to break even when thenegative electrode is closely wound or is bent at an acute angle.

The electrolytic copper foil is a foil obtained, for example, byimmersing a metallic drum in a nonaqueous electrolytic solution whichcontains copper ions dissolved therein, causing an electric current toflow while rotating the drum, thereby depositing copper on the surfaceof the drum, and peeling off the copper deposit. Copper may have beendeposited on the surfaces of the rolled copper foil by an electrolyticprocess. One or both surfaces of the copper foil may have undergone asurface-roughening treatment or a surface treatment (e.g., a chromatetreatment or undercoating with, for example, Ti, which are for forming alayer having a thickness of several nanometers to about 1 μm).

The current collector substrate is desired to further have the followingproperties.

(10-1) Average Surface Roughness (Ra)

The average surface roughness (Ra) of that surface of the currentcollector substrate on which a thin active-material film is to beformed, the roughness (Ra) being determined by the method described inJIS B0601-1994, is not particularly limited. However, the averagesurface roughness (Ra) thereof is generally 0.01 μm or higher,preferably 0.03 μm or higher, and is generally 1.5 μm or less,preferably 1.3 μm or less, more preferably 1.0 μm or less.

The reasons for this are as follows. When the current collectorsubstrate has an average surface roughness (Ra) within that range,satisfactory charge/discharge cycle characteristics can be expected.Furthermore, the interface between this current collector substrate anda thin active-material layer has an increased area to improve adhesionto the thin negative-electrode active-material layer. Incidentally,there is no particular upper limit on the average surface roughness (Ra)thereof. However, a current collector substrate having an averagesurface roughness (Ra) of 1.5 μm or less is usually employed becausecurrent collector substrates having an Ra exceeding 1.5 μm generally arenot easily available as foils having a thickness practical forbatteries.

(10-2) Tensile Strength

The tensile strength of a test piece is obtained by dividing the maximumtensile force required for the test piece to break by the sectional areaof the test piece. Tensile strength in the invention is determined usingthe same apparatus and method as those described in JIS Z2241 (Method ofTensile Test of Metallic Materials).

The tensile strength of the current collector substrate is notparticularly limited. However, the tensile strength thereof is generally50 N·mm⁻² or higher, preferably 100 N·mm⁻² or higher, more preferably150 N·mm⁻² or higher. The higher the tensile strength, the more thecurrent collector substrate is preferred. However, it is usuallydesirable that the tensile strength thereof should be 1,000 N·mm⁻² orless, from the standpoint of industrial availability.

So long as a current collector substrate having a high tensile strengthis used, this current collector substrate can be inhibited fromsuffering the cracking due to the expansion and contraction of the thinactive-material film which accompany charge/discharge. Satisfactorycycle characteristics can hence be obtained.

(10-3) 0.2% Proof Stress

“0.2% proof stress” is the magnitude of a load necessary for imparting aplastic (permanent) strain of 0.2%, and means that the material retainsa 0.2% deformation after a load of that magnitude which has been appliedthereto is removed. For determining 0.2% proof stress, use may be madeof the same apparatus and method as those for the tensile strength.

The 0.2% proof stress of the current collector substrate is notparticularly limited. However, the 0.2% proof stress thereof isgenerally 30 N·mm⁻² or higher, preferably 100 N·mm⁻² or higher,especially preferably 150 N·mm⁻² or higher. The higher the 0.2% proofstress, the more the current collector substrate is preferred. However,it is generally desirable that the 0.2% proof stress thereof should be900 N·mm⁻² or less, from the standpoint of industrial availability.

So long as a current collector substrate having a high 0.2% proof stressis used, this current collector substrate can be inhibited fromsuffering the plastic deformation due to the expansion and contractionof the thin active-material film which accompany charge/discharge.Satisfactory cycle characteristics can hence be obtained.

(10-4) Thickness of Current Collector

The current collector may have any desired thickness. However, thethickness thereof is generally 1 μm or more, preferably 3 μm or more,more preferably 5 μm or more, and is generally 1 mm or less, preferably100 μm or less, more preferably 50 μm or less.

When the thickness of the metal film is less than 1 μm, there are caseswhere coating fluid application thereto is difficult because of thereduced strength thereof. When the thickness thereof is larger than 100there are cases where the electrode shape obtained by, for example,winding is deformed.

Incidentally, the thin metal film may be a meshy material.

(11) Thickness Ratio Between Current Collector and Active-Material Layer

The thickness ratio between the current collector and theactive-material layer is not particularly limited. However, the value of“(thickness of the active-material layer on one surface just beforeimpregnation with nonaqueous electrolytic solution)/(thickness of thecurrent collector)” is generally 150 or less, preferably 20 or less,more preferably 10 or less, and is generally 0.1 or greater, preferably0.4 or greater, more preferably 1 or greater.

When the thickness ratio between the current collector and thenegative-electrode active-material layer exceeds that range, there arecases where this current collector is heated up by Joule's heat duringhigh-current-density charge/discharge. When the thickness ratiotherebetween is less than that range, there are cases where the batteryhas a reduced capacity because the proportion by volume of the currentcollector to the negative-electrode active material is high.

(12) Electrode Density

The structure of the electrode formed using a negative-electrode activematerial is not particularly limited. However, the density of the activematerial present on the current collector is preferably 1 g·cm⁻³ orhigher, more preferably 1.2 g·cm⁻³ or higher, even more preferably 1.3g·cm⁻³ or higher, especially preferably 1.5 g·cm⁻³ or higher, and ispreferably 3 g·cm⁻³ or less, more preferably 2.5 g·cm⁻³ or less, evenmore preferably 2.2 g·cm⁻³ or less, especially preferably 2 g·cm⁻³ orless.

When the density of the active material present on the current collectorexceeds that range, there are cases where bonding between the currentcollector and the negative-electrode active material is weak andseparation occurs between the electrode and the active material. Whenthe density thereof is less than that range, there are cases whereelectrical conductivity among the negative-electrode active-materialparticles decreases and this increases battery resistance.

(13) Binder

The binder for binding the negative-electrode active material is notparticularly limited so long as the binder is stable to the nonaqueouselectrolytic solution and to the solvent to be used for electrodeproduction.

Examples thereof include resinous polymers such as polyethylene,polypropylene, poly(ethylene terephthalate), poly(methyl methacrylate),polyimides, aromatic polyamides, cellulose, and nitrocellulose; rubberypolymers such as SBR (styrene/butadiene rubbers), isoprene rubbers,butadiene rubbers, fluororubbers, NBR (acrylonitrile/butadiene rubbers),and ethylene/propylene rubbers; styrene/butadiene/styrene blockcopolymers and products of hydrogenation thereof; thermoplasticelastomeric polymers such as EPDM (ethylene/propylene/dieneterpolymers), styrene/ethylene/butadiene/styrene copolymers, andstyrene/isoprene/styrene block copolymers and products of hydrogenationthereof; flexible resinous polymers such as syndiotactic1,2-polybutadiene, poly(vinyl acetate), ethylene/vinyl acetatecopolymers, and propylene/α-olefin copolymers; fluorochemical polymerssuch as poly(vinylidene fluoride), polytetrafluoroethylene, fluorinatedpoly(vinylidene fluoride), and polytetrafluoroethylene/ethylenecopolymers; and polymer compositions having the property of conductingalkali metal ions (especially lithium ions). One of these binders may beused alone, or any desired two or more thereof may be used incombination in any desired proportion.

The kind of the solvent to be used for forming a slurry is notparticularly limited so long as the negative-electrode active materialand binder and the thickener and conductive material which areoptionally used according to need can be dissolved or dispersed therein.Either an aqueous solvent or an organic solvent may be used.

Examples of the aqueous solvent include water and alcohols. Examples ofthe organic solvent include N-methylpyrrolidone (NMP),dimethylformamide, dimethylacetamide, methyl ethyl ketone,cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine,N,N-dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone,dimethyl ether, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, andhexane. Especially when an aqueous solvent is used, a dispersant or thelike is added in combination with the thickener to prepare a slurryusing a latex of, for example, SBR. One of those solvents may be usedalone, or any desired two or more thereof may be used in combination inany desired proportion.

The proportion of the binder to the negative-electrode active materialis generally 0.1% by mass or higher, preferably 0.5% by mass or higher,more preferably 0.6% by mass or higher, and is generally 20% by mass orless, preferably 15% by mass or less, more preferably 10% by mass orless, especially preferably 8% by mass or less.

When the proportion of the binder to the negative-electrode activematerial exceeds that range, there are cases where the proportion of thebinder which does not contribute to battery capacity increases and thisleads to a decrease in battery capacity. When the proportion thereof isless than that range, there are cases where the negative electrode has areduced strength and this is undesirable from the standpoint of batteryproduction.

Especially when the binder includes a rubbery polymer represented by SBRas the main component, the proportion of this binder to the activematerial is generally 0.1% by mass or higher, preferably 0.5% by mass orhigher, more preferably 0.6% by mass or higher, and is generally 5% bymass or less, preferably 3% by mass or less, more preferably 2% by massor less.

In the case where the binder includes a fluorochemical polymerrepresented by poly(vinylidene fluoride) as the main component, theproportion of this binder to the active material is 1% by mass orhigher, preferably 2% by mass or higher, more preferably 3% by mass orhigher, and is generally 15% by mass or less, preferably 10% by mass orless, more preferably 8% by mass or less.

A thickener is used generally for the purpose of regulating the slurryviscosity. The thickener is not particularly limited. Examples thereofinclude carboxymethyl cellulose, methyl cellulose, hydroxymethylcellulose, ethyl cellulose, poly(vinyl alcohol), oxidized starch,phosphorylated starch, casein, and salts of these. One of thesethickeners may be used alone, or any desired two or more thereof may beused in combination in any desired proportion.

In the case where such a thickener is further added, the proportion ofthe thickener to the negative-electrode active material is 0.1% by massor higher, preferably 0.5% by mass or higher, more preferably 0.6% bymass or higher, and is generally 5% by mass or less, preferably 3% bymass or less, more preferably 2% by mass or less. When the proportion ofthe thickener to the negative-electrode active material is less thanthat range, there are cases where applicability decreases considerably.When the proportion thereof exceeds that range, the proportion of theactive material in the negative-electrode active-material layer is low.There is hence a problem that the battery has a reduced capacity, andthere are cases where resistance among the particles of thenegative-electrode active material increases.

<2-4 Positive Electrode>

The positive electrode includes a current collector and apositive-electrode active-material layer disposed thereon. Thepositive-electrode active material is described below.

<2-4-1 Positive-Electrode Active Material>

The positive-electrode active material to be used in the positiveelectrode is explained below.

(1) Composition

The positive-electrode active material is not particularly limited solong as the active material is capable of electrochemically occludingand releasing lithium ions. For example, a substance which containslithium and at least one transition metal is preferred. Examples thereofinclude a lithium-transition metal composite oxide and alithium-containing transition metal/phosphoric acid compound.

Preferred examples of the transition metal of the lithium-transitionmetal composite oxide include V, Ti, Cr, Mn, Fe, Co, Ni, and Cu.Specific examples of the composite oxide include lithium-cobaltcomposite oxides such as LiCoO₂, lithium-manganese composite oxides suchas LiMnO₂, LiMn₂O₄, and Li₂MnO₄, and lithium-nickel composite oxidessuch as LiNiO₂. Examples of the composite oxide further include theselithium-transition metal composite oxides in which part of the atoms ofthe transition metals, which serve as main components of the compositeoxides, have been replaced with other metals, e.g., Al, Ti, V, Cr, Mn,Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, and Si. Examples thereof includelithium-cobalt-nickel composite oxides, lithium-cobalt-manganesecomposite oxides, lithium-nickel-manganese composite oxides, andlithium-nickel-cobalt-manganese composite oxides.

Specific examples of such replacement products includeLi_(1+a)Ni_(0.5)Mh_(0.5)O₂, Li_(1+a)Ni_(0.8)CO_(0.2)O₂,Li_(1+a)Ni_(0.85)Co_(0.10)Al_(0.05)O₂,Li_(1+a)Ni_(0.33)Co_(0.33)Mn_(0.33)O₂,Li_(1+a)Ni_(0.45)Co_(0.45)Mn_(0.1)O₂, Li_(1+a)Mn_(1.8)Al_(0.2)O₄,Li_(1+a)Mn_(1.5)Ni_(0.5)O₄, and xLi₂MnO₃.(1−x)Li_(1−a)MO₂ (M is atransition metal) (a satisfies 0<a≦3.0).

The lithium-containing transition metal/phosphoric acid compound can berepresented by Li_(x)MPO₄ (wherein M is at least one element selectedfrom the group consisting of the Group-4 to Group-11 transition metalsbelonging to the fourth period of the periodic table, and x satisfies0≦x<1.2). The transition metal (M) preferably is at least one elementselected from the group consisting of V, Ti, Cr, Mg, Zn, Ca, Cd, Sr, Ba,Co, Ni, Fe, Mn, and Cu, and more preferably is at least one elementselected from the group consisting of Co, Ni, Fe, and Mn. Examples ofthe compound include iron phosphate compounds such as LiFePO₄,Li₃Fe₂(PO₄)₃, and LiFeP₂O₇, cobalt phosphate compounds such as LiCoPO₄,manganese phosphate compounds such as LiMnPO₄, nickel phosphatecompounds such as LiNiPO₄, and these lithium-containing transitionmetal/phosphoric acid compounds in which part of the atoms of thetransition metals, which serves as main components of the compounds,have been replaced with other metals, e.g., Al, Ti, V, Cr, Mn, Fe, Co,Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, and Si. Especially suitable of these arelithium/manganese composite oxides such as LiMnO₂, LiMn₂O₄, and Li₂MnO₄and iron phosphate compounds such as LiFePO₄, Li₃Fe₂(PO₄)₃, andLiFeP₂O₇, because these compounds are less apt to suffer metaldissolution when in a high-temperature charged state and areinexpensive.

The expression “including LixMPO₄ as a basic composition” used abovemeans that not only compounds having a composition represented by theempirical formula but also compounds in which the Fe or other sites inthe crystal structure have been partly replaced by another element areincluded. Furthermore, that expression means that not only compoundshaving the stoichiometric composition but also compounds havingnon-stoichiometric compositions which include, for example, sites wherepart of the elements is deficient are included. It is preferred that theelement which replaces should be an element such as Al, Ti, V, Cr, Mn,Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, or Si. In the case where replacementby such an element is conducted, the degree of replacement is preferably0.1-5 mol %, more preferably 0.2-2.5 mol %.

The positive-electrode active materials described above may be usedalone or in combination of two or more thereof.

(2) Surface Coating

Use may also be made of a material composed of any of thepositive-electrode active materials and, adherent to the surfacethereof, a substance which differs in composition from thepositive-electrode active material as the main component (the adherentsubstance is hereinafter suitably referred to as “surface-adherentsubstance”). Examples of the surface-adherent substance include oxidessuch as aluminum oxide, silicon oxide, titanium oxide, zirconium oxide,magnesium oxide, calcium oxide, boron oxide, antimony oxide, and bismuthoxide, sulfates such as lithium sulfate, sodium sulfate, potassiumsulfate, magnesium sulfate, calcium sulfate, and aluminum sulfate, andcarbonates such as lithium carbonate, calcium carbonate, and magnesiumcarbonate.

Those surface-adherent substances each can be adhered to the surface ofa positive-electrode active material, for example, by: a method in whichthe substance is dissolved or suspended in a solvent and this solutionor suspension is infiltrated into the positive-electrode active materialand then dried; a method in which a precursor for the surface-adherentsubstance is dissolved or suspended in a solvent and this solution orsuspension is infiltrated into the positive-electrode active materialand then heated or otherwise treated to react the precursor; or a methodin which the substance is added to a precursor for thepositive-electrode active material and burned together with theprecursor.

The mass of the surface-adherent substance which is adherent to thesurface of the positive-electrode active material, based on the mass ofthe positive-electrode active material, is generally 0.1 ppm or more,preferably 1 ppm or more, more preferably 10 ppm or more, and isgenerally 20% or less, preferably 10% or less, more preferably 5% orless.

The surface-adherent substance can inhibit the nonaqueous electrolyticsolution from undergoing an oxidation reaction on the surface of thepositive-electrode active material, and an improvement in battery lifecan hence be attained. However, in case where the adhesion amount isless than that range, this effect is not sufficiently produced. When theadhesion amount exceeds that range, there are cases where thesurface-adherent substance inhibits lithium ions from going in and outand this results in an increase in resistance. Consequently, that rangeis preferred.

(3) Shape

The shape of the particles of the positive-electrode active material maybe any of massive, polyhedral, spherical, ellipsoidal, platy, acicular,columnar, and other shapes such as those in common use. Preferred ofthese is one in which the primary particles have aggregated to formsecondary particles and these secondary particles have a spherical orellipsoidal shape.

The reason for this is as follows. In electrochemical elements, theactive material in each electrode usually expands/contracts with thecharge/discharge of the element and, hence, a deterioration, such asactive-material breakage or conduction path breakage, that is caused bythe resultant stress is apt to occur. Consequently, a positive-electrodeactive material in which the primary particles have aggregated to formsecondary particles is preferable to an active material composed ofprimary particles only, since the particles in the former activematerial relieve the stress caused by expansion/contraction to preventthe deterioration.

Furthermore, particles of a spherical or ellipsoidal shape arepreferable to particles showing axial orientation, e.g., platyparticles, because the former particles are less apt to orient duringelectrode formation and hence this electrode is reduced inexpansion/contraction during charge/discharge, and because theseparticles are apt to be evenly mixed with a conductive material inelectrode production.

(4) Tap Density

The tap density of the positive-electrode active material is generally0.4 g·cm⁻³ or higher, preferably 0.6 g·cm⁻³ or higher, more preferably0.8 g·cm⁻³ or higher, especially preferably 1.0 g·cm⁻³ or higher, and isgenerally 4.0 g·cm⁻³ or less, preferably 3.8 g·cm⁻³ or less.

By using a composite metal oxide powder having a high tap density, apositive-electrode active-material layer having a high density can beformed. Consequently, in case where the tap density of thepositive-electrode active material is less than that range, not only itis necessary to use a larger amount of a dispersion medium and largeramounts of a conductive material and a binder when a positive-electrodeactive-material layer is formed, but also there are cases where theloading of the positive-electrode active material in thepositive-electrode active-material layer is limited, resulting in alimited battery capacity. The higher the tap density, the more thepositive-electrode active material is generally preferred. There is noparticular upper limit on the tap density thereof. However, when the tapdensity thereof is less than that range, there are cases where thediffusion of lithium ions which occurs within the positive-electrodeactive-material layer using the nonaqueous electrolytic solution as amedium becomes a rate-determining process and this is apt to reduce loadcharacteristics.

Tap density is determined by dropping a sample through a sieve having anopening size of 300 μm into a 20-cm³ tapping cell to fill the cellcapacity, subsequently conducting a tapping operation 1,000 times over astroke length of 10 mm using a powder densimeter (e.g., Tap Denser,manufactured by Seishin Enterprise Co., Ltd.), and calculating thedensity from the resultant volume of the sample and the mass thereof.The tap density calculated through this measurement is defined as thetap density of the positive-electrode active material according to theinvention.

(5) Median Diameter d50

The median diameter d50 (secondary-particle diameter in the case wherethe primary particles have aggregated to form secondary particles) ofthe particles of the positive-electrode active material can bedetermined also with a laser diffraction/scattering type particle sizedistribution analyzer.

The median diameter d50 thereof is generally 0.1 μm or more, preferably0.5 μm or more, more preferably 1 μm or more, especially preferably 3 μmor more, and is generally 20 μm or less, preferably 18 μm or less, morepreferably 16 μm or less, especially preferably 15 μm or less. When themedian diameter d50 thereof is less than that range, there are caseswhere a product having a high bulk density cannot be obtained. When themedian diameter d50 thereof exceeds that range, lithium diffusion withinindividual particles requires a longer period and this results in adecrease in battery characteristics. In addition, there are cases wherewhen such positive-electrode active-material particles are used inproducing a positive electrode for batteries, i.e., when the activematerial and other ingredients including a conductive material and abinder are slurried with a solvent and this slurry is applied in athin-film form, then streak lines or the like is caused.

Incidentally, it is possible to attain further improved loading duringpositive-electrode production by mixing, in any desired proportion, twoor more positive-electrode active materials differing in median diameterd50.

Median diameter d50 is determined using a 0.1% by mass aqueous solutionof sodium hexametaphosphate as a dispersion medium and using LA-920,manufactured by HORIBA Ltd., as a particle size distribution analyzer.After a 5-minute ultrasonic dispersing treatment is conducted, theparticles are examined at a measuring refractive index set at 1.24.

(6) Average Primary-Particle Diameter

In the case where the primary particles have aggregated to formsecondary particles, the average primary-particle diameter of thispositive-electrode active material is generally 0.03 μm or more,preferably 0.05 μm or more, more preferably 0.08 μm or more, especiallypreferably 0.1 μm or more, and is generally 5 μm or less, preferably 4μm or less, more preferably 3 μm or less, especially preferably 2 μm orless. In case where the average primary-particle diameter thereofexceeds that range, such primary particles are less apt to formspherical secondary particles, resulting in an adverse influence onpowder loading, and this material has a considerably reduced specificsurface area. There are hence cases where battery performances, e.g.,output characteristics, are apt to decrease. When the averageprimary-particle diameter thereof is less than that range, the crystalsusually are in an insufficiently grown state and, hence, there are caseswhere this positive-electrode active material makes the secondarybattery have reduced performances, e.g., poor charge/dischargereversibility.

Incidentally, average primary-particle diameter is determined through anexamination with a scanning electron microscope (SEM). Specifically,arbitrarily selected 50 primary-particle images in a photograph having amagnification of 10,000 diameters each are examined for the length ofthe longest segment of a horizontal line which extends across theprimary-particle image from one side to the other side of the boundary.These measured lengths are averaged to determine the average value.

(7) BET Specific Surface Area

The BET specific surface area of the positive-electrode active material,in terms of the value of specific surface area as determined by the BETmethod, is generally 0.1 m²·g⁻¹ or larger, preferably 0.2 m²·g⁻¹ orlarger, more preferably 0.3 m²·g⁻¹ or larger, and is generally 50 m²·g⁻¹or less, preferably 40 m²·g⁻¹ or less, more preferably 30 m²·g⁻¹ orless. In case where the value of the BET specific surface area thereofis less than that range, use of this positive-electrode active materialis apt to result in a decrease in battery performance. When the specificsurface area thereof exceeds that range, this positive-electrode activematerial is less apt to have a high tap density and there are caseswhere the applicability required for forming a positive-electrodeactive-material decreases.

The determination of BET specific surface area is made with a surfacearea meter (a fully automatic surface area measuring apparatusmanufactured by Ohkura Riken Co., Ltd.). A sample is preliminarily driedat 150° C. for 30 minutes in a nitrogen stream, and the specific surfacearea thereof is thereafter measured by the gas-flowing nitrogenadsorption BET one-point method using a nitrogen/helium mixture gasprecisely regulated so as to have a nitrogen pressure of 0.3 relative toatmospheric pressure. The specific surface area determined through thismeasurement is defined as the BET specific surface area of thepositive-electrode active material according to the invention.

(8) Processes for Producing Positive-Electrode Active Materials

Processes for producing positive-electrode active materials are notparticularly limited unless the processes depart from the spirit of theinvention. Examples thereof include several processes, and use may bemade of general processes for producing inorganic compounds.

Various processes are thought to be usable for producing, in particular,a spherical or ellipsoidal active material. Examples thereof include aprocess in which a transition metal source, e.g., a transition metalnitrate or sulfate, and a source of another element, which is usedaccording to need, are dissolved in or pulverized and dispersed in asolvent, e.g., water, and the pH of this solution or dispersion isregulated with stirring to produce spherical precursor particles. Theprecursor particles are recovered and optionally dried. Thereafter, alithium source, e.g., LiOH, Li₂CO₃, or LiNO₃, is added to the precursor,and the mixture is burned at a high temperature to obtain an activematerial.

Another example is a process in which a transition metal source, e.g., atransition metal nitrate, sulfate, hydroxide, or oxide, and a source ofanother element, which is used according to need, are dissolved in orpulverized and dispersed in a solvent, e.g., water, and this solution ordispersion is dried and molded with a spray dryer or the like to obtainspherical or ellipsoidal precursor particles. A lithium source, e.g.,LiOH, Li₂CO₃, or LiNO₃, is added to the precursor, and the mixture isburned at a high temperature to obtain an active material.

Still another process is a process in which a transition metal source,e.g., a transition metal nitrate, sulfate, hydroxide, or oxide, alithium source, e.g., LiOH, Li₂CO₃, or LiNO₃, and a source of anotherelement, which is used according to need, are dissolved in or pulverizedand dispersed in a solvent, e.g., water, and this solution or dispersionis dried and molded with a spray dryer or the like to obtain sphericalor ellipsoidal precursor particles. This precursor is burned at a hightemperature to obtain an active material.

<2-4-2 Electrode Structure and Production Process>

The configuration of the positive electrode to be used in the inventionand a process for producing the positive electrode are explained below.

(1) Process for Producing Positive Electrode

The positive electrode is produced by forming a positive-electrodeactive-material layer including positive-electrode active-materialparticles and a binder on a current collector. The production of thepositive electrode using a positive-electrode active material can beconducted by any known method. Namely, a positive-electrode activematerial and a binder are mixed together by a dry process optionallytogether with a conductive material, thickener, etc., and this mixtureis formed into a sheet and press-bonded to a positive-electrode currentcollector. Alternatively, those materials are dissolved or dispersed ina liquid medium to obtain a slurry, and this slurry is applied to apositive-electrode current collector and dried. Thus, apositive-electrode active-material layer is formed on the currentcollector, and the positive electrode can be thereby obtained.

The content of the positive-electrode active material in thepositive-electrode active-material layer is preferably 80% by mass orhigher, more preferably 82% by mass or higher, especially preferably 84%by mass or higher. The upper limit thereof is preferably 99% by mass orless, more preferably 98% by mass or less. When the content of thepositive-electrode active material in the positive-electrodeactive-material layer is too low, there are cases where an insufficientelectrical capacity results. Conversely, when the content thereof is toohigh, there are cases where the positive electrode has insufficientstrength. Incidentally, one positive-electrode active-material powderaccording to the invention may be used alone, or any desired two or morepositive-electrode active-material powders according to the inventionwhich differ in composition or powder property may be used incombination in any desired proportion.

(2) Conductive Material

As the conductive material, a known conductive material can be used atwill. Examples thereof include metallic materials such as copper andnickel; graphites such as natural graphites and artificial graphites;carbon blacks such as acetylene black; and carbonaceous materials suchas amorphous carbon, e.g., needle coke. One of these materials may beused alone, or any desired two or more thereof may be used incombination in any desired proportion.

The conductive material may be used so that the material is incorporatedin the positive-electrode active-material layer in an amount which isgenerally 0.01% by mass or more, preferably 0.1% by mass or more, morepreferably 1% by mass or more, and is generally 50% by mass or less,preferably 30% by mass or less, more preferably 15% by mass or less.When the content thereof is less than that range, there are cases whereelectrical conductivity is insufficient. When the content thereofexceeds that range, there are cases where a decrease in battery capacityresults.

(3) Binder

The binder to be used for producing the positive-electrodeactive-material layer is not particularly limited so long as the binderis a material which is stable to the nonaqueous electrolytic solutionand to the solvent to be used for electrode production.

In the case where the layer is to be formed through coating fluidapplication, any binder may be used so long as it is a material which issoluble or dispersible in the liquid medium for use in electrodeproduction. Examples thereof include resinous polymers such aspolyethylene, polypropylene, poly(ethylene terephthalate), poly(methylmethacrylate), aromatic polyamides, cellulose, and nitrocellulose;rubbery polymers such as SBR (styrene/butadiene rubbers), NBR(acrylonitrile/butadiene rubbers), fluororubbers, isoprene rubbers,butadiene rubbers, and ethylene/propylene rubbers; thermoplasticelastomeric polymers such as styrene/butadiene/styrene block copolymersor products of hydrogenation thereof, EPDM (ethylene/propylene/dieneterpolymers), styrene/ethyl ene/butadiene/ethyl ene copolymers, andstyrene/isoprene/styrene block copolymers or products of hydrogenationthereof; flexible resinous polymers such as syndiotactic1,2-polybutadiene, poly(vinyl acetate), ethylene/vinyl acetatecopolymers, and propylene/α-olefin copolymers; fluorochemical polymerssuch as poly(vinylidene fluoride) (PVdF), polytetrafluoroethylene,fluorinated poly(vinylidene fluoride), andpolytetrafluoroethylene/ethylene copolymers; and polymer compositionshaving the property of conducting alkali metal ions (especially lithiumions). One of these substances may be used alone, or any desired two ormore thereof may be used in combination in any desired proportion.

The proportion of the binder in the positive-electrode active-materiallayer is generally 0.1% by mass or higher, preferably 1% by mass orhigher, more preferably 3% by mass or higher, and is generally 50% bymass or less, preferably 30% by mass or less, more preferably 10% bymass or less, especially preferably 8% by mass or less. When theproportion of the binder is less than that range, there are cases wherethe positive-electrode active material cannot be sufficiently held andthe positive electrode has insufficient mechanical strength, resultingin a decrease in battery performance, e.g., cycle characteristics. Whenthe proportion thereof exceeds that range, there are cases where suchtoo high a proportion leads to a decrease in battery capacity orelectrical conductivity.

(4) Liquid Medium

The kind of the liquid medium to be used for forming a slurry is notparticularly limited so long as the liquid medium is a solvent in whichthe positive-electrode active material, conductive material, and binderand a thickener, which is used according to need, can be dissolved ordispersed. Either an aqueous solvent or an organic solvent may be used.

Examples of the aqueous medium include water and mixed solvents composedof an alcohol and water. Examples of the organic medium include:aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such asbenzene, toluene, xylene, and methylnaphthalene; heterocyclic compoundssuch as quinoline and pyridine; ketones such as acetone, methyl ethylketone, and cyclohexanone; esters such as methyl acetate and methylacrylate; amines such as diethylenetriamine andN,N-dimethylaminopropylamine; ethers such as diethyl ether andtetrahydrofuran (THF); amides such as N-methylpyrrolidone (NMP),dimethylformamide, and dimethylacetamide; and aprotic polar solventssuch as hexamethylphosphoramide and dimethyl sulfoxide. One of thesemedia may be used alone, or any desired two or more thereof may be usedin combination in a desired proportion.

(5) Thickener

In the case where an aqueous medium is used as the liquid medium forslurry formation, it is preferred to produce a slurry using a thickenerand a latex of, for example, a styrene/butadiene rubber (SBR). Thethickener is used in order to regulate the viscosity of the slurry.

The thickener is not limited unless the effects of the invention areconsiderably lessened thereby. Examples thereof include carboxymethylcellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose,poly(vinyl alcohol), oxidized starch, phosphorylated starch, casein, andsalts of these. One of these thickeners may be used alone, or anydesired two or more thereof may be used in combination in any desiredproportion.

In the case where such a thickener is further added, it is desirablethat the proportion of the thickener to the active material should begenerally 0.1% by mass or higher, preferably 0.5% by mass or higher,more preferably 0.6% by mass or higher, and be generally 5% by mass orless, preferably 3% by mass or less, more preferably 2% by mass or less.When the proportion of the thickener to the active material is less thanthat range, there are cases where applicability decreases considerably.When the proportion thereof exceeds that range, the proportion of theactive material in the positive-electrode active-material layer is low.There is hence a problem that the battery has a reduced capacity, andthere are cases where resistance among the particles of thepositive-electrode active material increases.

(6) Densification by Pressing

It is preferred that the positive-electrode active-material layerobtained by coating fluid application and drying should be densified bypressing with a handpress, roller press, or the like in order toheighten the loading density of the positive-electrode active material.The density of the positive-electrode active-material layer ispreferably 1 g·cm⁻³ or higher, more preferably 1.5 g·cm⁻³ or higher,especially preferably 2 g·cm⁻³ or higher, and is preferably 4 g·cm⁻³ orless, more preferably 3.5 g·cm⁻³ or less, especially preferably 3 g·cm⁻³or less.

When the density of the positive-electrode active-material layer exceedsthat range, there are cases where the nonaqueous electrolytic solutionis less apt to infiltrate into around the current collector/activematerial interface and the battery has reduced charge/dischargecharacteristics especially at a high current density. When the densitythereof is less than that range, there are cases where electricalconductivity among the active-material particles decreases and thisincreases battery resistance.

(7) Current Collector

The material of the positive-electrode current collector is notparticularly limited, and a known one can be used at will. Examplesthereof include metallic materials such as aluminum, stainless steel,nickel-plated materials, titanium, and tantalum; and carbonaceousmaterials such as carbon cloths and carbon papers. Of these, metallicmaterials are preferred. Especially preferred is aluminum.

In the case of a metallic material, examples of the shape of the currentcollector include metal foils, metal cylinders, metal coils, metalplates, thin metal films, expanded metals, punching metals, and metalfoam. In the case of a carbonaceous material, examples of the collectorshape include carbon plates, thin carbon films, and carbon cylinders. Ofthese, a thin metal film is preferred. The thin film may be suitablyprocessed into a mesh form.

Although the current collector may have any desired thickness, thethickness thereof is generally 1 μm or more, preferably 3 μm or more,more preferably 5 μm or more, and is generally 1 mm or less, preferably100 μm or less, more preferably 50 μm or less. When the thin film has athickness less than that range, there are cases where this thin film isinsufficient in the strength required of current collectors. When thethin film has a thickness larger than that range, there are cases wherethis film has impaired handleability.

The thickness ratio between the current collector and thepositive-electrode active-material layer is not particularly limited.However, the value of (thickness of the positive-electrodeactive-material layer on one surface just before impregnation withelectrolytic solution)/(thickness of the current collector) ispreferably 20 or less, more preferably 15 or less, most preferably 10 orless, and the lower limit thereof is preferably 0.5 or greater, morepreferably 0.8 or greater, most preferably 1 or greater. When thethickness ratio exceeds that range, there are cases where the currentcollector is heated up by Joule's heat during high-current-densitycharge/discharge. When the thickness ratio is less than that range,there are cases where the proportion by volume of the current collectorto the positive-electrode active material increases to reduce thecapacity of the battery.

<2-5. Separator>

A separator is generally interposed between the positive electrode andthe negative electrode in order to prevent short-circuiting. In thiscase, the nonaqueous electrolytic solution of the invention is usuallyinfiltrated into the separator.

The material and shape of the separator are not particularly limited,and known separators can be employed at will unless the effects of theinvention are considerably lessened thereby. In particular, use may bemade of separators constituted of materials stable to the nonaqueouselectrolytic solution of the invention, such as resins, glass fibers,and inorganic materials. It is preferred to use a separator which is inthe form of a porous sheet, nonwoven fabric, or the like and hasexcellent liquid retentivity.

As the material of the resinous or glass-fiber separators, use can bemade of, for example, polyolefins such as polyethylene andpolypropylene, polytetrafluoroethylene, polyethersulfones, glassfilters, and the like. Preferred of these are glass filters andpolyolefins. More preferred are polyolefins. One of these materials maybe used alone, or any desired two or more thereof may be used incombination in any desired proportion.

The separator may have any desired thickness. However, the thicknessthereof is generally 1 μm or more, preferably 5 μm or more, morepreferably 10 μm or more, and is generally 50 μm or less, preferably 40μm or less, more preferably 30 μm or less. When the thickness of theseparator is less than that range, there are cases where insulatingproperties or mechanical strength decreases. When the thickness thereofexceeds that range, there are cases where not only battery performances,e.g., rate characteristics, decrease but also the nonaqueous-electrolytesecondary battery as a whole has a reduced energy density.

In the case where a porous material such as, e.g., a porous sheet ornonwoven fabric is used as the separator, this separator may have anydesired porosity. However, the porosity thereof is generally 20% orhigher, preferably 35% or higher, more preferably 45% or higher, and isgenerally 90% or lower, preferably 85% or lower, more preferably 75% orlower. In case where the porosity thereof is less than that range, thisseparator tends to have increased film resistance, resulting in impairedrate characteristics. In case where the porosity thereof is higher thanthat range, this separator tends to have reduced mechanical strength,resulting in reduced insulating properties.

The separator may have any desired average pore diameter. However, theaverage pore diameter thereof is generally 0.5 μm or less, preferably0.2 μm or less, and is generally 0.05 μm or more. In case where theaverage pore diameter thereof exceeds that range, short-circuiting isapt to occur. When the average pore diameter thereof is less than thatrange, there are cases where this separator has increased filmresistance, resulting in reduced rate characteristics.

On the other hand, examples of the inorganic materials which may be usedinclude oxides such as alumina and silicon dioxide, nitrides such asaluminum nitride and silicon nitride, and sulfates such as bariumsulfate and calcium sulfate. Such materials of a particulate shape orfibrous shape may be used.

With respect to form, a separator of a thin film form may be used, suchas nonwoven fabric, woven fabric, or microporous film. Suitableseparators of a thin film form have a pore diameter of 0.01-1 μm and athickness of 5-50 μm. Besides such a separator in an independent thinfilm form, use can be made of a separator obtained by forming acomposite porous layer containing particles of the inorganic materialusing a resinous binder on a surface layer of the positive electrodeand/or negative electrode. Examples thereof include to form a porouslayer from alumina particles having a 90% particle diameter smaller than1 μm on both surfaces of the positive electrode using a fluororesin as abinder.

<2-6. Battery Design>

[Electrode Group]

The electrode group may be either of: an electrode group having amultilayer structure in which the positive-electrode plate and thenegative-electrode plate have been superposed through the separator; andan electrode group having a wound structure in which thepositive-electrode plate and the negative-electrode plate have beenspirally wound through the separator. The proportion of the volume ofthe electrode group to the internal volume of the battery (hereinafterreferred to as electrode group proportion) is generally 40% or higher,preferably 50% or higher, and is generally 90% or less, preferably 80%or less. In case where the electrode group proportion is less than thatrange, the battery has reduced capacity. In case where the electrodegroup proportion exceeds that range, the battery has too small a spacevolume and undergoes an increase in internal pressure when the batteryis heated up to cause members to expand or a liquid component of theelectrolyte to have a heightened vapor pressure. There are hence caseswhere this battery is reduced in various characteristics includingcharge/discharge cycle performance and high-temperature storability, andwhere the gas release valve, which releases the internal pressureoutside, works.

[Structure for Current Collection]

The structure for current collection is not particularly limited.However, for more effectively attaining the improvement in dischargecharacteristics which is brought about by the nonaqueous electrolyticsolution of the invention, it is preferred to employ a structure reducedin the resistance of wiring parts and joint parts. In the case whereinternal resistance has been reduced in this manner, use of thenonaqueous electrolytic solution of the invention produces the effectsthereof especially satisfactorily.

In the case of an electrode group assembled into the multilayerstructure described above, a structure obtained by bundling the metalliccore parts of respective electrode layers and welding the bundled partsto terminals is suitable. When each electrode has a large area, thisresults in increased internal resistance. In this case, it is preferredto dispose a plurality of terminals in each electrode to reduce theresistance. In the case of an electrode group having the wound structuredescribed above, a plurality of lead structures may be disposed on eachof the positive electrode and negative electrode and bundled into aterminal. Thus, internal resistance can be reduced.

[Outer Case]

The material of the outer case to be used is not particularly limited solong as the material is stable to the nonaqueous electrolytic solutionto be used. Specifically, use is made of a metal, e.g., a nickel-platedsteel sheet, stainless steel, aluminum, an aluminum alloy, or amagnesium alloy, or a laminated film composed of a resin and an aluminumfoil. From the standpoint of weight reduction, a metal such as aluminumor an aluminum alloy or a laminated film is suitable.

Examples of the outer case employing any of those metals include: anouter case formed by fusion-bonding the metal to itself by laserwelding, resistance welding, or ultrasonic welding to constitute asealed structure; and an outer case formed by caulking the metal througha resinous gasket to constitute a caulked structure. Examples of theouter case employing the laminated film include an outer case having asealed structure obtained by thermally fusion-bonding the resin layer toitself. A resin which is different from the resin used in the laminatedfilm may be interposed between the resin layers in order to enhancesealing properties. Especially in the case where resin layers arethermally fusion-bonded to each other through collector terminals toform a sealed structure, either a resin having polar groups or a resinwhich has been modified by introducing polar groups thereinto issuitable for use as the resin to be interposed, because metal/resinbonding is involved.

[Protective Element]

Examples of the protective element include a PTC (positive temperaturecoefficient), which increases in resistance upon abnormal heating-up orwhen an excessive current flows, a temperature fuse, a thermister, and avalve (current breaker valve) which, upon abnormal heating-up, breaksthe current flowing through the circuit, on the basis of an abruptincrease in the internal pressure or internal temperature of thebattery. It is preferred to select such a protective element which doesnot work under ordinary high-current use conditions. From the standpointof high output, it is more preferred to employ a design which preventsabnormal heating-up and thermal run-away even without a protectiveelement.

[Case]

The nonaqueous-electrolyte secondary battery of the invention usually isfabricated by housing the nonaqueous electrolytic solution, negativeelectrode, positive electrode, separator, etc. in a case. This case isnot limited, and a known case can be employed at will unless thisconsiderably lessens the effects of the invention.

Specifically, although the case may be made of any desired material, useis generally made of nickel-plated iron, stainless steel, aluminum or analloy thereof, nickel, titanium, or the like.

The case may have any desired shape. For example, the case may be any ofthe cylindrical type, prismatic type, laminate type, coin type, largetype, and the like.

EXAMPLES

The invention will be explained below in more detail by reference toExamples and Comparative Examples. However, the invention should not beconstrued as being limited to the following Examples.

Example 1 Production of Negative Electrode

To 98 parts by mass of artificial-graphite powder KS-44 (trade name;manufactured by Timcal) were added 100 parts by mass of an aqueousdispersion of sodium carboxymethyl cellulose (concentration of sodiumcarboxymethyl cellulose, 1% by mass) as a thickener and 2 parts by massof an aqueous dispersion of a styrene/butadiene rubber (concentration ofstyrene/butadiene rubber, 50% by mass) as a binder. The ingredients weremixed together by means of a disperser to obtain a slurry. The slurryobtained was applied to one surface of a copper foil having a thicknessof 10 μm and dried. This coated foil was pressed by rolling with apressing machine, and a piece of a shape having an active-material layersize with a width of 30 mm and a length of 40 mm and having an uncoatedarea with a width of 5 mm and a length of 9 mm was cut out of the rolledsheet. Thus, a negative electrode was obtained.

[Production of Positive Electrode]

Ninety percents by mass Li(Ni_(1/3)Mn_(1/3)CO_(1/3))O₂ (LNMC) as apositive-electrode active material was mixed with 5% by mass acetyleneblack as a conductive material and 5% by mass poly(vinylidene fluoride)(PVdF) as a binder in N-methylpyrrolidone solvent to obtain a slurry.The slurry obtained was applied to one surface of an aluminum foilhaving a thickness of 15 μm and coated beforehand with a conduction aid,and dried. This coated foil was rolled with a pressing machine to athickness of 80 vim, and a piece of a shape having an active-materiallayer size with a width of 30 mm and a length of 40 mm and having auncoated area with a width of 5 mm and a length of 9 mm was cut out ofthe rolled sheet. Thus, a positive electrode was obtained.

[Production of Electrolytic Solution]

In a dry argon atmosphere, 99.5 parts by mass of a mixture of ethylenecarbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate(EMC) (volume ratio, 30:30:40) was mixed with 0.5 parts by mass ofvinylene carbonate (VC). Subsequently, sufficiently dried LiFSO₃ andLiPF₆ were dissolved therein so as to result in proportions thereof of0.01 mol/L and 1 mol/L, respectively. Thus, an electrolytic solution wasobtained.

[Production of Lithium Secondary Battery]

The positive electrode and negative electrode described above and aseparator made of polyethylene were superposed in the order of negativeelectrode/separator/positive electrode to produce a battery element.This battery element was inserted into a bag constituted of a laminatedfilm obtained by coating both surfaces of aluminum (thickness, 40 μm)with a resin layer, with the terminals of the positive and negativeelectrodes projecting outward. Thereafter, the electrolytic solution wasintroduced into the bag, and this bag was vacuum-sealed to produce asheet battery which came into a fully charged state at 4.1 V. Thebattery design is shown in Table 1.

[Evaluation of Initial Discharge Capacity]

The lithium secondary battery was evaluated in the state of beingsandwiched between glass plates in order to enhance contact between theelectrodes. At 25° C., this battery was charged to 4.1 V at a constantcurrent corresponding to 0.2 C and then discharged to 3.0 V at aconstant current of 0.2 C. Two cycles of this charge/discharge wereconducted to stabilize the battery. In the third cycle, the battery wascharged to 4.1 V at a constant current of 0.2 C, subsequently charged ata constant voltage of 4.1 V until the current value became 0.05 C, andthen discharged to 3.0 V at a constant current of 0.2 C. Thereafter, inthe fourth cycle, the battery was charged to 4.1 V at a constant currentof 0.2 C, subsequently charged at a constant voltage of 4.1 V until thecurrent value became 0.05 C, and then discharged to 3.0 V at a constantcurrent of 0.2 C to determine initial discharge capacity. Here, “1 C”means a current value at which the reference capacity of the battery isdischarged over 1 hour; “5 C” means the current value which is 5 timesthe current of 1 C, “0.1 C” means the current value which is 1/10 thecurrent of 1 C, and “0.2 C” means the current value which is ⅕ thecurrent of 1 C. The results of the evaluation are shown in Table 2.

[Evaluation of −30° C. Impedance]

The battery which had undergone the evaluation of initial capacity wascharged at 25° C. and a constant current of 0.2 C to a half of theinitial discharge capacity. At −30° C., an alternating-voltage amplitudeof 10 mV was applied to the battery to measure the impedance of thebattery. Thus, real resistance at 0.08 Hz was determined. The results ofthe evaluation are shown in Table 2.

Example 2

In a dry argon atmosphere, 99.5 parts by mass of a mixture of ethylenecarbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate(EMC) (volume ratio, 30:30:40) was mixed with 0.5 parts by mass ofvinylene carbonate (VC). Subsequently, sufficiently dried LiFSO₃ andLiPF₆ were dissolved therein so as to result in proportions thereof of0.1 mol/L and 0.9 mol/L, respectively. Thus, an electrolytic solutionwas obtained. A sheet-form lithium secondary battery was produced andevaluated in the same manners as in Example 1. The battery design isshown in Table 1, and the results of the evaluation are shown in Table2.

Example 3

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.3 mol/Land 0.7 mol/L, respectively. The battery design is shown in Table 1, andthe results of the evaluation are shown in Table 2.

Example 4

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.5 mol/Land 0.5 mol/L, respectively. The battery design is shown in Table 1, andthe results of the evaluation are shown in Table 2.

Example 5

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedtetraethylammonium fluorosulfonate (TEAFSO₃) and LiPF₆ therein so as toresult in proportions thereof of 0.05 mol/L and 1 mol/L, respectively.The battery design is shown in Table 1, and the results of theevaluation are shown in Table 2.

Example 6

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedtetrabuthylammonium fluorosulfonate (TBAFSO₃) and LiPF₆ therein so as toresult in proportions thereof of 0.05 mol/L and 1 mol/L, respectively.The battery design is shown in Table 1, and the results of theevaluation are shown in Table 2.

Example 7

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedtetraethylphosphonium fluorosulfonate (TEPFSO₃) and LiPF₆ therein so asto result in proportions thereof of 0.05 mol/L and 1 mol/L,respectively. The battery design is shown in Table 1, and the results ofthe evaluation are shown in Table 2.

Example 8

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedtetrabuthylphosphonium fluorosulfonate (TBPFSO₃) and LiPF₆ therein so asto result in proportions thereof of 0.05 mol/L and 1 mol/L,respectively. The battery design is shown in Table 1, and the results ofthe evaluation are shown in Table 2.

Comparative Example 1

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃therein so as to result in a proportion thereof of 1 mol/L. The batterydesign is shown in Table 1, and the results of the evaluation are shownin Table 2.

Comparative Example 2

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.7 mol/Land 0.3 mol/L, respectively. The battery design is shown in Table 1, andthe results of the evaluation are shown in Table 2.

Comparative Example 3

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.55 mol/Land 0.45 mol/L, respectively. The battery design is shown in Table 1,and the results of the evaluation are shown in Table 2.

Comparative Example 4

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 1, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiPF₆therein so as to result in a proportion thereof of 1 mol/L. The batterydesign is shown in Table 1, and the results of the evaluation are shownin Table 2.

TABLE 1 Positive- electrode Electrolyte Solvent Additive active material(concen- (volume (parts by (evaluation [FSO₃]/ tration) ratio) mass)voltage) [PF₆] Example 1 LiFSO₃ EC:DMC:EMC VC LNMC 0.010 (0.01 M)(30:30:40) (0.5) (4.1 V) LiPF₆ (1.0 M) Example 2 LiFSO₃ EC:DMC:EMC VCLNMC 0.111 (0.1 M) (30:30:40) (0.5) (4.1 V) LiPF₆ (0.9 M) Example 3LiFSO₃ EC:DMC:EMC VC LNMC 0.429 (0.3 M) (30:30:40) (0.5) (4.1 V) LiPF₆(0.7 M) Example 4 LiFSO₃ EC:DMC:EMC VC LNMC 1.000 (0.5 M) (30:30:40)(0.5) (4.1 V) LiPF₆ (0.5 M) Example 5 TEAFSO₃ EC:DMC:EMC VC LNMC 0.050(0.05 M) (30:30:40) (0.5) (4.1 V) LiPF₆ (1.0 M) Example 6 TBAFSO₃EC:DMC:EMC VC LNMC 0.050 (0.05 M) (30:30:40) (0.5) (4.1 V) LiPF₆ (1.0 M)Example 7 TEPFSO₃ EC:DMC:EMC VC LNMC 0.050 (0.05 M) (30:30:40) (0.5)(4.1 V) LiPF₆ (1.0 M) Example 8 TBPFSO₃ EC:DMC:EMC VC LNMC 0.050 (0.05M) (30:30:40) (0.5) (4.1 V) LiPF₆ (1.0 M) Comparative LiFSO₃ EC:DMC:EMCVC LNMC ∞ Example 1 (1.0 M) (30:30:40) (0.5) (4.1 V) Comparative LiFSO₃EC:DMC:EMC VC LNMC 2.333 Example 2 (0.7 M) (30:30:40) (0.5) (4.1 V)LiPF₆ (0.3 M) Comparative LiFSO₃ EC:DMC:EMC VC LNMC 1.222 Example 3(0.55 M) (30:30:40) (0.5) (4.1 V) LiPF₆ (0.45 M) Comparative LiPF₆EC:DMC:EMC VC LNMC 0.000 Example 4 (1.0 M) (30:30:40) (0.5) (4.1 V)

TABLE 2 Initial impedance Initial (relative value; the value dischargein Comparative Example capacity (mAh/g) 4 being taken as 1) Example 1140.9 0.78 Example 2 141.2 0.67 Example 3 141.2 0.61 Example 4 139.00.85 Example 5 140.8 0.86 Example 6 141.8 0.82 Example 7 139.2 0.76Example 8 139.8 0.77 Comparative Example 1 132.8 22.32 ComparativeExample 2 132.3 2.24 Comparative Example 3 137.2 1.15 ComparativeExample 4 140.2 1.00

Example 9

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.5 parts by mass ofvinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.05 mol/Land 1 mol/L, respectively. The battery design is shown in Table 3.

[Evaluation of Initial Discharge Capacity]

The lithium secondary battery was evaluated in the state of beingsandwiched between glass plates in order to enhance contact between theelectrodes. At 25° C., this battery was charged to 4.1 V at a constantcurrent corresponding to 0.2 C and then discharged to 3.0 V at aconstant current of 0.2 C. Two cycles of this charge/discharge wereconducted to stabilize the battery. In the third cycle, the battery wascharged to 4.1 V at a constant current of 0.2 C, subsequently charged ata constant voltage of 4.1 V until the current value became 0.05 C, andthen discharged to 3.0 V at a constant current of 0.2 C. Thereafter, inthe fourth cycle, the battery was charged to 4.1 V at a constant currentof 0.2 C, subsequently charged at a constant voltage of 4.1 V until thecurrent value became 0.05 C, and then discharged to 3.0 V at a constantcurrent of 0.2 C to determine initial discharge capacity.

[Evaluation of Initial 25° C. Output]

The battery which had undergone the evaluation of initial dischargecapacity was charged at 25° C. and a constant current of 0.2 C to a halfof the initial discharge capacity. This battery was discharged at 25° C.at each of 1 C, 2 C, 3 C, 5 C, 10 C, 15 C, and 20 C, and the voltage wasmeasured at the time when 10 seconds had passed since the dischargeinitiation. The area of the triangle surrounded by the current-voltageline and the lower-limit voltage (3 V) was regarded as output (W). Therelative value (%) of the output was calculated, with the output valueat 25° C. in Comparative Example 5 being taken as 100. The results ofthe battery evaluation are shown in Table 4.

[Evaluation of Initial −30° C. Output]

The battery which had undergone the evaluation of initial dischargecapacity was charged at 25° C. and a constant current of 0.2 C to a halfof the initial discharge capacity. This battery was discharged at −30°C. at each of 0.2 C, 0.4 C, 0.8 C, 1 C, and 2 C, and the voltage wasmeasured at the time when 2 seconds had passed since the dischargeinitiation. The area of the triangle surrounded by the current-voltageline and the lower-limit voltage (3 V) was regarded as output (W). Therelative value (%) of the output was calculated, with the output valueat −30° C. in Comparative Example 5 being taken as 100. The results ofthe battery evaluation are shown in Table 4.

Example 10

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.5 parts by mass ofvinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.1 mol/Land 1 mol/L, respectively. The battery design is shown in Table 3, andthe results of the evaluation are shown in Table 4.

Example 11

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.5 parts by mass ofvinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.2 mol/Land 1 mol/L, respectively. The battery design is shown in Table 3, andthe results of the evaluation are shown in Table 4.

Example 12

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.5 parts by mass ofvinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.3 mol/Land 0.7 mol/L, respectively. The battery design is shown in Table 3, andthe results of the evaluation are shown in Table 4.

Example 13

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.5 parts by mass ofmonofluoroethylene carbonate (MFEC) and then dissolving sufficientlydried LiFSO₃ and LiPF₆ therein so as to result in proportions thereof of0.1 mol/L and 1 mol/L, respectively. The battery design is shown inTable 3, and the results of the evaluation are shown in Table 4.

Example 14

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.8 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.2 parts by mass of1-propene-1,3-sultone (PRES) and then dissolving sufficiently driedLiFSO₃ and LiPF₆ therein so as to result in proportions thereof of 0.1mol/L and 1 mol/L, respectively. The battery design is shown in Table 3,and the results of the evaluation are shown in Table 4.

Example 15

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.8 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.2 parts by mass ofsuccinonitrile (SN) and then dissolving sufficiently dried LiFSO₃ andLiPF₆ therein so as to result in proportions thereof of 0.1 mol/L and 1mol/L, respectively. The battery design is shown in Table 3, and theresults of the evaluation are shown in Table 4.

Comparative Example 5

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.5 parts by mass ofvinylene carbonate (VC) and then dissolving sufficiently dried LiPF₆therein so as to result in a proportion thereof of 1 mol/L. The batterydesign is shown in Table 3, and the results of the evaluation are shownin Table 4.

Comparative Example 6

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) and 0.5 parts by mass of1-propene-1,3-sultone (PRES) and then dissolving sufficiently driedLiPF₆ therein so as to result in a proportion thereof of 1 mol/L. Thebattery design is shown in Table 3, and the results of the evaluationare shown in Table 4.

TABLE 3 Positive- electrode Electrolyte Solvent Additive active material(concen- (volume (parts by (evaluation [FSO₃]/ tration) ratio) mass)voltage) [PF₆] Example 9 LiFSO₃ EC:DMC:EMC VC LNMC 0.050 (0.05 M)(30:30:40) (0.5) (4.1 V) LiPF₆ (1.0 M) Example 10 LiFSO₃ EC:DMC:EMC VCLNMC 0.100 (0.1 M) (30:30:40) (0.5) (4.1 V) LiPF₆ (1.0 M) Example 11LIFSO₃ EC:DMC:EMC VC LNMC 0.200 (0.2 M) (30:30:40) (0.5) (4.1 V) LiPF₆(1.0 M) Example 12 LiFSO₃ EC:DMC:EMC VC LNMC 0.429 (0.3 M) (30:30:40)(0.5) (4.1 V) LiPF₆ (0.7 M) Example 13 LiFSO₃ EC:DMC:EMC MFEC LNMC 0.100(0.1 M) (30:30:40) (0.5) (4.1 V) LiPF₆ (1.0 M) Example 14 LiFSO₃EC:DMC:EMC PRES LNMC 0.100 (0.1 M) (30:30:40) (0.2) (4.1 V) LiPF₆ (1.0M) Example 15 LiFSO₃ EC:DMC:EMC SN LNMC 0.100 (0.1 M) (30:30:40) (0.2)(4.1 V) LiPF₆ (1.0 M) Comparative LiFSO₃ EC:DMC:EMC VC LNMC ∞ Example 5(1.0 M) (30:30:40) (0.5) (4.1 V) Comparative LiPF₆ EC:DMC:EMC PRES LNMC∞ Example 6 (1.0 M) (30:30:40) (0.5) (4.1 V)

TABLE 4 Initial 25° C. Initial −30° C. Output (relative Output (relativevalue; the value in value; the value in Comparative Example ComparativeExample 5 being taken as 1) 5 being taken as 1) Example 9 1.02 1.14Example 10 1.03 1.21 Example 11 1.04 1.24 Example 12 1.04 1.53 Example13 1.04 1.27 Example 14 1.02 1.16 Example 15 1.02 1.14 ComparativeExample 5 1.00 1.00 Comparative Example 6 0.60 0.80

Example 16

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing a mixture of ethylene carbonate (EC),dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (volumeratio, 30:30:40) and then dissolving sufficiently dried LiFSO₃ and LiPF₆therein so as to result in proportions thereof of 0.05 mol/L and 1mol/L, respectively. The battery design is shown in Table 5.

[Evaluation of Initial Discharge Capacity]

The lithium secondary battery was evaluated in the state of beingsandwiched between glass plates in order to enhance contact between theelectrodes. At 25° C., this battery was charged to 4.1 V at a constantcurrent corresponding to 0.2 C and then discharged to 3.0 V at aconstant current of 0.2 C. Two cycles of this charge/discharge wereconducted to stabilize the battery. In the third cycle, the battery wascharged to 4.1 V at a constant current of 0.2 C, subsequently charged ata constant voltage of 4.1 V until the current value became 0.05 C, andthen discharged to 3.0 V at a constant current of 0.2 C. Thereafter, inthe fourth cycle, the battery was charged to 4.1 V at a constant currentof 0.2 C, subsequently charged at a constant voltage of 4.1 V until thecurrent value became 0.05 C, and then discharged to 3.0 V at a constantcurrent of 0.2 C to determine initial discharge capacity. Here, “1 C”means a current value at which the reference capacity of the battery isdischarged over 1 hour; “5 C” means the current value which is 5 timesthe current of 1 C, “0.1 C” means the current value which is 1/10 thecurrent of 1 C, and “0.2 C” means the current value which is ⅕ thecurrent of 1 C. The results of the battery evaluation are shown in Table6.

[Evaluation of High-Temperature Cycle Characteristics]

At 60° C., the battery which had undergone the evaluation of initialcapacity was charged to 4.1 V at a constant current of 2 C and thendischarged to 3.0 V at a constant current of 2 C. This operation wastaken as one cycle, and 500 cycles were conducted. At 25° C., thebattery which had undergone the cycling was charged to 4.1 V and wasthen discharged to 3.0 V at a constant current of 0.2 C to determine theafter-cycling capacity. The results of the battery evaluation are shownin Table 6.

[Evaluation of 25° C. Output after High-Temperature Cycling]

The battery which had undergone the evaluation of high-temperature cyclecharacteristics was charged at 25° C. and a constant current of 0.2 C toa half of the initial discharge capacity. This battery was discharged at25° C. at each of 1 C, 2 C, 3 C, 5 C, 10 C, 15 C, and 20 C, and thevoltage was measured at the time when 10 seconds had passed since thedischarge initiation. The area of the triangle surrounded by thecurrent-voltage line and the lower-limit voltage (3 V) was regarded asoutput (W). The relative value (%) of the output was calculated, withthe output value at 25° C. in Comparative Example 5 being taken as 100.The results of the battery evaluation are shown in Table 6.

[Evaluation of −30° C. Output after High-Temperature Cycling]

The battery which had undergone the evaluation of high-temperature cyclecharacteristics was charged at 25° C. and a constant current of 0.2 C toa half of the initial discharge capacity. This battery was discharged at−30° C. at each of 0.2 C, 0.4 C, 0.8 C, 1 C, and 2 C, and the voltagewas measured at the time when 2 seconds had passed since the dischargeinitiation. The area of the triangle surrounded by the current-voltageline and the lower-limit voltage (3 V) was regarded as output (W). Therelative value (%) of the output was calculated, with the output valueat −30° C. in Comparative Example 7 being taken as 100. The results ofthe battery evaluation are shown in Table 6.

[Evaluation of High-Temperature Storability]

The battery which had undergone the test for evaluating initialdischarge capacity was charged to 4.1 V at a constant current of 0.2 Cand then charged at a constant voltage of 4.1 V until the current valuebecame 0.05 C. This battery was stored at 60° C. for 20 days, cooled toroom temperature, and then discharged at 25° C. to 3 V at a constantcurrent of 0.2 C to determine the residual capacity. Thereafter, therecovery capacity of this battery was determined through a test in whichthe battery was charged to 4.1 V at a constant current of 0.2 C,subsequently charged at a constant voltage of 4.1 V until the currentvalue became 0.05 C, and then discharged to 3 V at a constant current of0.2 C. Finally, the capacity retention after storage (%) was determinedby calculating (recovery capacity)÷(initial discharge capacity)×100. Theresults of the battery evaluation are shown in Table 6.

Example 17

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing a mixture of ethylene carbonate (EC),dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (volumeratio, 30:30:40) and then dissolving sufficiently dried LiFSO₃ and LiPF₆therein so as to result in proportions thereof of 0.1 mol/L and 1 mol/L,respectively. This battery was subjected to the same evaluation as inExample 16. The battery design is shown in Table 5, and the results ofthe evaluation are shown in Table 6.

Example 18

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing a mixture of ethylene carbonate (EC),dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (volumeratio, 30:30:40) and then dissolving sufficiently dried LiFSO₃, LiPO₂F₂,and LiPF₆ therein so as to result in proportions thereof of 0.05 mol/L,0.05 mol/L, and 1 mol/L, respectively. This battery was subjected to thesame evaluation as in Example 16. The battery design is shown in Table5, and the results of the evaluation are shown in Table 6.

Example 19

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by mixing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by mass ofvinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃,LiPO₂F₂, and LiPF₆ therein so as to result in proportions thereof of0.05 mol/L, 0.05 mol/L, and 1 mol/L, respectively. This battery wassubjected to the same evaluation as in Example 16. The battery design isshown in Table 5, and the results of the evaluation are shown in Table6.

Comparative Example 7

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by preparing a mixture of ethylene carbonate (EC),dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (volumeratio, 30:30:40) and then dissolving sufficiently dried LiPF₆ therein soas to result in a proportion thereof of 1 mol/L. This battery wassubjected to the same evaluation as in Example 16. The battery design isshown in Table 5, and the results of the evaluation are shown in Table6.

TABLE 5 Positive- electrode Electrolyte Solvent Additive active material(concen- (volume (parts by (evaluation [FSO₃]/ tration) ratio) mass)voltage) [PF₆] Example 16 LiFSO₃ EC:DMC:EMC none LNMC 0.050 (0.05 M)(30:30:40) (4.1 V) LiPF₆ (1.0 M) Example 17 LiFSO₃ EC:DMC:EMC none LNMC0.100 (0.1 M) (30:30:40) (4.1 V) LiPF₆ (1.0 M) Example 18 LiFSO₃EC:DMC:EMC none LNMC 0.050 (0.05 M) (30:30:40) (4.1 V) LiPF₆ (1.0 M)LiPO₂F₂ (0.05 M) Example 19 LiFSO₃ EC:DMC:EMC VC LNMC 0.050 (0.05 M)(30:30:40) (0.5) (4.1 V) LiPF₆ (1.0 M) LiPO₂F₂ (0.05 M) ComparativeLiPF₆ EC:DMC:EMC none LNMC 0.000 Example 7 (1.0 M) (30:30:40) (4.1 V)

TABLE 6 Evaluation of cycle characteristics Relative 25° C. Relative−30° C. output after cycling output after cycling (W); the 25° C. (W);the −30° C. output after cycling output after cycling Evaluation ofhigh-temperature storability Initial battery Capacity after inComparative in Comparative Residual Recovery Capacity capacity 500cycles Example 7 being Example 7 being capacity capacity retention(mAh/g) (mAh/g) taken as 1 taken as 1 (mAh/g) (mAh/g) (%) Example 16138.1 118.5 1.11 1.13 122.5 132.9 96.2 Example 17 138.1 119.3 1.12 1.11123.8 133.7 96.8 Example 18 138.7 120.5 1.28 1.27 124.1 133.4 96.2Example 19 138.0 123.5 1.24 1.06 124.6 133.2 96.5 Comparative Example 7138.1 111.0 1.00 1.00 120.0 131.6 95.3

Example 20 Production of Positive Electrode

Ninety percents by mass iron lithium phosphate (LiFePO₄, LFP) as apositive-electrode active material was mixed with 5% by mass acetyleneblack as a conductive material and 5% by mass poly(vinylidene fluoride)(PVdF) as a binder in N-methylpyrrolidone solvent to obtain a slurry.The slurry obtained was applied to one surface of an aluminum foilhaving a thickness of 15 μm and coated beforehand with a conduction aid,and dried. This coated foil was pressed by rolling with a pressingmachine, and a piece of a shape having an active-material layer sizewith a width of 30 mm and a length of 40 mm and having a uncoated areawith a width of 5 mm and a length of 9 mm was cut out of the rolledsheet. Thus, a positive electrode was obtained.

[Production of Electrolytic Solution]

In a dry argon atmosphere, 99.5 parts by mass of a mixture of ethylenecarbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate(EMC) (volume ratio, 30:30:40) was mixed with 0.5 parts by mass ofvinylene carbonate (VC). Subsequently, sufficiently dried LiFSO₃ andLiPF₆ were dissolved therein so as to result in proportions thereof of0.05 mol/L and 1 mol/L, respectively. Thus, an electrolytic solution wasobtained.

[Production of Lithium Secondary Battery]

A sheet battery was produced in the same manner as in Example 1, exceptthat the positive electrode and electrolytic solution described abovewere used. The battery design is shown in Table 7.

[Evaluation of Initial Discharge Capacity]

The lithium secondary battery was evaluated in the state of beingsandwiched between glass plates in order to enhance contact between theelectrodes. At 25° C., this battery was charged to 4.0 V at a constantcurrent corresponding to 0.2 C and then discharged to 2.5 V at aconstant current of 0.1 C. Two cycles of this charge/discharge wereconducted to stabilize the battery. In each of the third to sixthcycles, the battery was charged to 4.0 V at a constant current of 0.2 C,subsequently charged at a constant voltage of 4.0 V until the currentvalue became 0.05 C, and then discharged to 2.5 V at a constant currentof 0.2 C. Thereafter, in the seventh cycle, the battery was charged to4.0 V at a constant current of 0.2 C, subsequently charged at a constantvoltage of 4.0 V until the current value became 0.05 C, and thendischarged to 2.5 V at a constant current of 0.2 C to determine initialdischarge capacity.

[Evaluation of −30° C. Output]

The battery which had undergone the evaluation of initial capacity wascharged at 25° C. and a constant current of 0.2 C to a half of theinitial discharge capacity. This battery was discharged at −30° C. for10 seconds at each of 0.2 C, 0.4 C, 0.8 C, 1 C, and 2 C, and the voltagewas measured at the time when the 10 seconds had passed. The area of thetriangle surrounded by the current-voltage line and the lower-limitvoltage (3 V) was regarded as output (W). The relative value (%) of theoutput was calculated, with the output value at −30° C. in ComparativeExample 6 being taken as 100. The results of the battery evaluation areshown in Table 8.

[Evaluation of −30° C. Output after High-Temperature Cycling]

At 60° C., the battery which had undergone the evaluation of initialoutput was charged to 4.1 V at a constant current of 2 C and thendischarged to 3.0 V at a constant current of 2 C. This operation wastaken as one cycle, and 500 cycles were conducted. The battery which hadundergone the cycling was charged at 25° C. and a constant current of0.2 C to a half of the initial discharge capacity. This battery wasdischarged at −30° C. at each of 0.2 C, 0.4 C, 0.8 C, 1 C, and 2 C, andthe voltage was measured at the time when 2 seconds had passed since thedischarge initiation. The area of the triangle surrounded by thecurrent-voltage line and the lower-limit voltage (3 V) was regarded asoutput (W). The relative value (%) of the output was calculated, withthe output value at −30° C. in Comparative Example 6 being taken as 100.The results of the battery evaluation are shown in Table 8.

Comparative Example 8

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 20, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiPF₆therein so as to result in a proportion thereof of 1 mol/L. The batterydesign is shown in Table 7, and the results of the evaluation are shownin Table 8.

Comparative Example 9

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 20, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedlithium trifluoroacetate (LiCF₃CO₂) and LiPF₆ therein so as to result inproportions thereof of 0.05 mol/L and 1 mol/L, respectively. The batterydesign is shown in Table 7, and the results of the evaluation are shownin Table 8.

Comparative Example 10

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 20, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedlithium trifluoromethanesulfonate (LiCF₃SO₃) and LiPF₆ therein so as toresult in proportions thereof of 0.05 mol/L and 1 mol/L, respectively.The battery design is shown in Table 7, and the results of theevaluation are shown in Table 8.

Comparative Example 11

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 20, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedlithium bisoxalatoborate (LiB(C₂O₄)₂, LiBOB) and LiPF₆ therein so as toresult in proportions thereof of 0.05 mol/L and 1 mol/L, respectively.The battery design is shown in Table 7, and the results of theevaluation are shown in Table 8.

Comparative Example 12

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 20, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedlithium bistrifluoromethylsulfonylimide (LiN(SO₂CF₃)₂, LiTFSI) and LiPF₆therein so as to result in proportions thereof of 0.05 mol/L and 1mol/L, respectively. The battery design is shown in Table 7, and theresults of the evaluation are shown in Table 8.

TABLE 7 Electrolyte Solvent Additive Positive- (concen- (volume (partsby electrode [FSO₃]/ tration) ratio) mass) active material [PF₆] Example20 LiFSO₃ EC:DMC:EMC VC LFP 0.050 (0.05 M) (30:30:40) (0.5) LiPF₆ (1.0M) Comparative LiPF₆ EC:DMC:EMC VC LFP 0.000 Example 8 (1.0 M)(30:30:40) (0.5) Comparative LiCF₃CO₂ EC:DMC:EMC VC LFP 0.000 Example 9(0.05 M) (30:30:40) (0.5) LiPF₆ (1.0 M) Comparative LiCF₃SO₃ EC:DMC:EMCVC LFP 0.000 Example 10 (0.05 M) (30:30:40) (0.5) LiPF₆ (1.0 M)Comparative LiBOB EC:DMC:EMC VC LFP 0.000 Example 11 (0.05 M) (30:30:40)(0.5) LiPF₆ (1.0 M) Comparative LiTFSI EC:DMC:EMC VC LFP 0.000 Example12 (0.05 M) (30:30:40) (0.5) LiPF₆ (1.0 M)

TABLE 8 Relative −30° C. Relative initial −30° C. output after cycling;output; the initial −30° C. the −30° C. output output in Comparativeafter cycling in Comparative Example 8 being Example 8 being taken as 1taken as 1 Example 20 1.20 1.21 Comparative 1.00 1.00 Example 8Comparative 1.13 0.81 Example 9 Comparative 1.13 1.04 Example 10Comparative 0.66 0.89 Example 11 Comparative 0.95 0.99 Example 12

Example 21 Production of Positive Electrode

Eighty percents by mass lithium manganate (Li_(1.1) M_(1.9)Al_(0.1)O₄,LMO) and 20% by mass Li_(1.15)Ni_(0.45)Mn_(0.45)Co_(0.10)O₂ (Co-lessLNMC) were mixed as positive-electrode active materials with 5% by massacetylene black as a conductive material and 5% by mass poly(vinylidenefluoride) (PVdF) as a binder in N-methylpyrrolidone solvent to obtain aslurry. The slurry obtained was applied to one surface of an aluminumfoil having a thickness of 15 μm and coated beforehand with a conductionaid, and dried. This coated foil was pressed by rolling with a pressingmachine, and a piece of a shape having an active-material layer sizewith a width of 30 mm and a length of 40 mm and having an uncoated areawith a width of 5 mm and a length of 9 mm was cut out of the rolledsheet. Thus, a positive electrode was obtained.

[Production of Electrolytic Solution]

In a dry argon atmosphere, a mixture of ethylene carbonate (EC),dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (volumeratio, 30:30:40) was prepared. Subsequently, sufficiently dried LiFSO₃and LiPF₆ were dissolved therein so as to result in proportions thereofof 0.1 mol/L and 1 mol/L, respectively. Thus, an electrolytic solutionwas obtained.

[Production of Lithium Secondary Battery]

A sheet battery was produced in the same manner as in Example 1, exceptthat the positive electrode and electrolytic solution described abovewere used. The battery design is shown in Table 9.

[Evaluation of Initial Discharge Capacity]

The lithium secondary battery was evaluated in the state of beingsandwiched between glass plates in order to enhance contact between theelectrodes. At 25° C., this battery was charged to 4.2 V at a constantcurrent corresponding to 0.1 C and then discharged to 3.0 V at aconstant current of 0.1 C. In the second and third cycles, the batterywas charged to 4.2 V at 0.33 C, subsequently charged at a constantvoltage of 4.2 V until the current value became 0.05 C, and thendischarged to 3.0 V at a constant current of 0.33 C. The initialdischarge capacity was determined from the results obtained in thethird-cycle discharge.

[Evaluation of Initial Output]

The battery which had undergone the evaluation of initial capacity wascharged at 25° C. and a constant current of 0.33 C to a half of theinitial discharge capacity. This battery was discharged at 25° C. for 10seconds at each of 1 C, 2 C, 3 C, 5 C, 10 C, 15 C, and 20 C, and thevoltage was measured at the time when the 10 seconds had passed. Thearea of the triangle surrounded by the current-voltage line and thelower-limit voltage (3 V) was regarded as output (W).

[Evaluation of High-Temperature Storability]

The battery which had undergone the test for evaluating initialdischarge capacity was charged to 4.2 V at a constant current of 0.33 Cand then charged at a constant voltage of 4.2 V until the current valuebecame 0.05 C. This battery was stored at 75° C. for 24 hours, cooled toroom temperature, and then discharged at 25° C. to 3.0 V at a constantcurrent of 0.33 C to determine the residual capacity. Thereafter, therecovery capacity of this battery was determined through a test in whichthe battery was charged to 4.2 V at a constant current of 0.33 C,subsequently charged at a constant voltage of 4.2 V until the currentvalue became 0.05 C, and then discharged to 3.0 V at a constant currentof 0.33 C. Finally, the capacity retention after storage (%) wasdetermined by calculating (recovery capacity)÷(initial dischargecapacity)×100. The results of the battery evaluation are shown in Table10.

[Evaluation of Output after High-Temperature Storage]

The battery which had undergone the high-temperature storage test wascharged at 25° C. and a constant current of 0.33 C to a half of theinitial discharge capacity. This battery was discharged at 25° C. ateach of 1 C, 2 C, 3 C, 5 C, 10 C, 15 C, and 20 C, and the voltage wasmeasured at the time when 10 seconds had passed since the dischargeinitiation. The area of the triangle surrounded by the current-voltageline and the lower-limit voltage (3 V) was regarded as output (W).Finally, the relative value of the output obtained after thehigh-temperature storage test, when the value of initial output wastaken as 1, was calculated. The results of the battery evaluation areshown in Table 10.

Example 22

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 21, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing ethylene carbonate (EC),dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (volumeratio, 30:30:40) and then dissolving sufficiently dried LiFSO₃, lithiumbisoxalatoborate (LiB(C₂O₄)₂, LiBOB), and LiPF₆ therein so as to resultin proportions thereof 0.1 mol/L, 0.1 mol/L, and 1 mol/L, respectively.The battery design is shown in Table 9, and the results of theevaluation are shown in Table 10.

Example 23

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 21, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.1 mol/Land 1 mol/L, respectively. The battery design is shown in Table 9, andthe results of the evaluation are shown in Table 10.

Example 24

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 21, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 1.0 part by mass ofhexamethylene diisocyanate (HMDI) and then dissolving sufficiently driedLiFSO₃ and LiPF₆ therein so as to result in proportions thereof of 0.1mol/L and 1 mol/L, respectively. The battery design is shown in Table 9,and the results of the evaluation are shown in Table 10.

Comparative Example 13

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 21, except that an electrolytic solution wasobtained in a dry argon atmosphere by preparing a mixture of ethylenecarbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate(EMC) (volume ratio, 30:30:40) and then dissolving sufficiently driedLiPF₆ therein so as to result in a proportion thereof of 1 mol/L. Thebattery design is shown in Table 9, and the results of the evaluationare shown in Table 10.

Comparative Example 14

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 21, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving LiPF₆ therein so as toresult in a proportion thereof of 1 mol/L. The battery design is shownin Table 9, and the results of the evaluation are shown in Table 10.

TABLE 9 Electrolyte Solvent Additive Positive- (concen- (volume (partsby electrode [FSO₃]/ tration) ratio) mass) active material [PF₆] Example21 LiFSO₃ EC:DMC:EMC none LMO 0.100 (0.1 M) (30:30:40) Co-less LNMCLiPF₆ (1.0 M) Example 22 LiFSO₃ EC:DMC:EMC none LMO 0.100 (0.1 M)(30:30:40) Co-less LNMC LiBOB (0.1 M) LiPF₆ (1.0 M) Example 23 LiFSO₃EC:DMC:EMC VC LMO 0.100 (0.1 M) (30:30:40) (0.5) Co-less LNMC LiPF₆ (1.0M) Example 24 LiFSO₃ EC:DMC:EMC HMDI LMO 0.100 (0.1 M) (30:30:40) (1.0)Co-less LNMC LiPF₆ (1.0 M) Comparative LiPF₆ EC:DMC:EMC none LMO 0.000Example 13 (1.0 M) (30:30:40) Co-less LNMC Comparative LiPF₆ EC:DMC:EMCVC LMO 0.000 Example 14 (1.0 M) (30:30:40) (0.5) Co-less LNMC

TABLE 10 Relative 25° C. output after Residual Recovery storage; thecapacity capacity Capacity 25° C. output after 60° C. after 60° C.retention before storage storage storage after storage being taken(mAh/g) (mAh/g) (%) as 1 Example 21 90.7 97.4 77.8 0.90 Example 22 91.198.6 80.9 0.96 Example 23 92.0 97.8 78.1 0.90 Example 24 87.0 96.4 90.41.07 Comparative 83.8 92.2 71.9 0.83 Example 13 Comparative 86.3 93.173.6 0.85 Example 14

Example 25

A sheet-form lithium secondary battery was produced in the same manneras in Example 1, except that an electrolytic solution was obtained in adry argon atmosphere by mixing 99.5 parts by mass of a mixture ofethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methylcarbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by mass ofvinylene carbonate (VC) and then dissolving sufficiently dried LiFSO₃and LiPF₆ therein so as to result in proportions thereof of 0.1 mol/Land 1 mol/L, respectively, and that the battery came into a fullycharged state at 4.4 V. The battery design is shown in Table 11.

[Evaluation of Initial Discharge Capacity]

The lithium secondary battery was evaluated in the state of beingsandwiched between glass plates in order to enhance contact between theelectrodes. At 25° C., this battery was charged to 4.1 V at a constantcurrent corresponding to 0.2 C and then discharged to 3.0 V at aconstant current of 0.2 C. Two cycles of this charge/discharge wereconducted to stabilize the battery. In the third cycle, the battery wascharged to 4.4 V at a constant current of 0.2 C, subsequently charged ata constant voltage of 4.4 V until the current value became 0.05 C, andthen discharged to 3.0 V at a constant current of 0.2 C. Thereafter, inthe fourth cycle, the battery was charged to 4.4 V at a constant currentof 0.2 C, subsequently charged at a constant voltage of 4.4 V until thecurrent value became 0.05 C, and then discharged to 3.0 V at a constantcurrent of 0.2 C to determine initial discharge capacity.

[Evaluation of High-Temperature Storability]

The battery which had undergone the test for evaluating initialdischarge capacity was charged to 4.4 V at a constant current of 0.2 Cand then charged at a constant voltage of 4.4 V until the current valuebecame 0.05 C. This battery was stored at 75° C. for 120 hours,subsequently cooled, and then discharged at 25° C. to 3 V at a constantcurrent of 0.2 C to determine the residual capacity. Thereafter, therecovery capacity of this battery was determined through a test in whichthe battery was charged to 4.4 V at a constant current of 0.2 C,subsequently charged at a constant voltage of 4.4 V until the currentvalue became 0.05 C, and then discharged to 3 V at a constant current of0.2 C. Finally, the capacity retention after storage (%) was determinedby calculating (recovery capacity)±(initial discharge capacity)×100. Theresults of the evaluation are shown in Table 12.

Example 26

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 25, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and 0.5 parts by mass of 1,3-propanesultone(PS) and then dissolving sufficiently dried LiFSO₃ and LiPF₆ therein soas to result in proportions thereof of 0.1 mol/L and 1 mol/L,respectively. The battery design is shown in Table 11, and the resultsof the evaluation are shown in Table 12.

Example 27

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 25, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedtetraethylammonium fluorosulfonate (TEAFSO₃) and LiPF₆ therein so as toresult in proportions thereof of 0.05 mol/L and 1 mol/L, respectively.The battery design is shown in Table 11, and the results of theevaluation are shown in Table 12.

Example 28

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 25, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedtetraethylammonium fluorosulfonate (TEAFSO₃) and LiPF₆ therein so as toresult in proportions thereof of 0.1 mol/L and 1 mol/L, respectively.The battery design is shown in Table 11, and the results of theevaluation are shown in Table 12.

Example 29

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 25, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedtetrabuthylammonium fluorosulfonate (TBAFSO₃) and LiPF₆ therein so as toresult in proportions thereof of 0.05 mol/L and 1 mol/L, respectively.The battery design is shown in Table 11, and the results of theevaluation are shown in Table 12.

Example 30

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 25, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently driedtetrabuthylammonium fluorosulfonate (TBAFSO₃) and LiPF₆ therein so as toresult in proportions thereof of 0.1 mol/L and 1 mol/L, respectively.The battery design is shown in Table 11, and the results of theevaluation are shown in Table 12.

Comparative Example 15

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 25, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99.5 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and then dissolving sufficiently dried LiPF₆therein so as to result in a proportion thereof of 1 mol/L. The batterydesign is shown in Table 11, and the results of the evaluation are shownin Table 12.

Comparative Example 16

A sheet-form lithium secondary battery was produced and evaluated in thesame manners as in Example 25, except that an electrolytic solution wasobtained in a dry argon atmosphere by mixing 99 parts by mass of amixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (volume ratio, 30:30:40) with 0.5 parts by massof vinylene carbonate (VC) and 0.5 parts by mass of1,3-propanesultone(PS) and then dissolving sufficiently dried LiPF₆therein so as to result in a proportion thereof of 1 mol/L. The batterydesign is shown in Table 11, and the results of the evaluation are shownin Table 12.

TABLE 11 Positive- electrode Electrolyte Solvent Additive activematerial (concen- (volume (parts by (evaluation [FSO₃]/ tration) ratio)mass) voltage) [PF₆] Example 25 LIFSO₃ EC:DMC:EMC VC LNMC 0.100 (0.1 M)(30:30:40) (0.5) (4.4 V) LiPF₆ (1.0 M) Example 26 LiFSO₃ EC:DMC:EMC VCLNMC 0.100 (0.1 M) (30:30:40) (0.5) (4.4 V) LiPF₆ PS (1.0 M) (0.5)Example 27 TEAFSO₃ EC:DMC:EMC VC LNMC 0.050 (0.05 M) (30:30:40) (0.5)(4.4 V) LiPF₆ (1.0 M) Example 28 TEAFSO₃ EC:DMC:EMC VC LNMC 0.100 (0.1M) (30:30:40) (0.5) (4.4 V) LiPF₆ (1.0 M) Example 29 TBAFSO₃ EC:DMC:EMCVC LNMC 0.050 (0.05 M) (30:30:40) (0.5) (4.4 V) LiPF₆ (1.0 M) Example 30TBAFSO₃ EC:DMC:EMC VC LNMC 0.100 (0.1 M) (30:30:40) (0.5) (4.4 V) LiPF₆(1.0 M) Comparative LiPF₆ EC:DMC:EMC VC LNMC 0.000 Example 15 (1.0 M)(30:30:40) (0.5) (4.4 V) Comparative LiPF₆ EC:DMC:EMC VC LNMC 0.000Example 16 (1.0 M) (30:30:40) (0.5) (4.4 V) PS (0.5)

TABLE 12 After 75° C. 120-hour storage Relative −30° C. Battery outputafter storage; capacity the −30° C. output before Residual RecoveryCapacity before storage in storage capacity capacity retentionComparative Example (mAh/g) (mAh/g) (mAh/g) (%) 14 being taken as 1Example 25 179.1 138.0 157.1 77.1 1.13 Example 26 179.6 139.5 159.0 77.71.10 Example 27 177.6 130.3 151.0 73.4 1.18 Example 28 176.1 132.8 152.375.4 1.13 Example 29 178.0 132.4 153.0 74.4 1.13 Example 30 177.8 136.7156.4 76.9 1.17 Comparative 178.9 123.7 147.3 69.1 1.00 Example 15Comparative 179.3 127.9 150.4 71.3 0.76 Example 16

As apparent from the Examples and Comparative Examples given above, thebatteries each employing a nonaqueous electrolytic solution according tothe invention are superior in initial discharge capacity, impedancecharacteristics, and output characteristics to the batteries eachemploying a nonaqueous electrolytic solution which is not a nonaqueouselectrolytic solution according to the invention. In addition, theformer batteries are satisfactory also with respect to cyclecharacteristics, storage durability, and output characteristicsdetermined after the durability test. It can be seen that the inventionproduces excellent effects on overall battery characteristics. Namely,those characteristics are improved by regulating the ratio of the molarcontent of FSO₃ derived from the fluorosulfonic acid salt ([FSO₃]) tothe molar content of PF₆ derived from LiPF₆ ([PF₆]), i.e., [FSO₃]/[PF₆],so as to be within the range according to the invention. The cation usedin the fluorosulfonic acid salt may be any of metals represented bylithium, a quaternary ammonium, and a quaternary phosphonium. Even whenaids such as, for example, a carbonate having an unsaturated bond, acarbonate having fluorine atoms, a nitrile compound, an isocyanocompound, and a cyclic sulfonic acid ester have been added, the effectsaccording to the invention are maintained. Furthermore, even whenanother electrolyte has been incorporated besides LiPF₆ and thefluorosulfonic acid salt, the effects of the invention are produced solong as the amount of the optional electrolyte is within the rangeaccording to the invention. Moreover, it can be understood that theeffects of the invention are produced even when the invention is appliedto various battery voltages or to any electrode active material.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof. This application is basedon a Japanese patent application filed on Feb. 12, 2010 (Application No.2010-029484), the contents thereof being incorporated herein byreference.

INDUSTRIAL APPLICABILITY

According to the nonaqueous electrolytic solution of the invention, itis possible to improve the initial charge capacity and input/outputcharacteristics of a nonaqueous-electrolyte secondary battery. Thenonaqueous-electrolyte secondary battery employing the nonaqueouselectrolytic solution of the invention has a high capacity retention andexcellent input/output performance even after a durability test, such asa high-temperature storage test or a cycle test, and further hasexcellent low-temperature input/output characteristics. This batteryhence is useful. Consequently, the nonaqueous electrolytic solution ofthe invention and the nonaqueous-electrolyte secondary battery whichemploys the electrolytic solution can be used in various knownapplications. Examples thereof include notebook type personal computers,pen-input personal computers, mobile personal computers, electronic-bookplayers, portable telephones, portable facsimile telegraphs, portablecopiers, portable printers, headphone stereos, video movie cameras,liquid-crystal TVs, handy cleaners, portable CD players, mini-diskplayers, transceivers, electronic pocketbooks, electronic calculators,memory cards, portable tape recorders, radios, backup power sources,motors, motor vehicles, motor cycles, bicycles fitted with a motor,bicycles, illuminators, toys, game machines, clocks and watches, powertools, stroboscopes, cameras, power sources for load leveling, and powersources for storing natural energy.

The invention claimed is:
 1. A nonaqueous electrolytic solution fornonaqueous-electrolyte secondary battery which comprises: a nonaqueoussolvent; LiPF₆; and a fluorosulfonic acid salt represented by formula(1):M(FSO₃)_(x) wherein M is a metal atom, N(R)₄, or P(R)₄ wherein R iseither an organic group having 1-12 carbon atoms or a hydrogen atomwherein not all of the four R's are hydrogen atoms, the R's may be thesame or different, and a part or all of the four R's may form a ring incooperation with the nitrogen atom or phosphorus atom to which the R'shave been bonded; when M is a metal atom, x indicates the valence of themetal atom M and is an integer of 1 or larger; and when M is N(R)₄ orP(R)₄, x is 1, wherein the nonaqueous electrolytic solution furthercomprises at least one selected from the group consisting of a cycliccarbonate having a fluorine atom, a cyclic carbonate havingcarbon-carbon unsaturated bond, a cyclic sulfonic acid ester compound, acompound having cyano group, a diisocyanate compound, a fluorophosphoricacid lithium salt other than LiPF₆, a lithium imide salt, and a lithiumsalt having an oxalic acid group, and wherein the ratio of the molarcontent of FSO₃ in the nonaqueous electrolytic solution to the molarcontent of PF₆ in the nonaqueous electrolytic solution is 0.0005-0.5. 2.The nonaqueous electrolytic solution for nonaqueous-electrolytesecondary battery according to claim 1, wherein the fluorosulfonic acidsalt represented by formula (1) is lithium fluorosulfonate.
 3. Thenonaqueous electrolytic solution for nonaqueous-electrolyte secondarybattery according to claim 1, which comprises the cyclic carbonatehaving a fluorine atom in the nonaqueous electrolytic solution in anamount of 0.001-85% by mass.
 4. The nonaqueous electrolytic solution fornonaqueous-electrolyte secondary battery according to claim 1, whichcomprises the cyclic carbonate having a carbon-carbon unsaturated bondin the nonaqueous electrolytic solution in an amount of 0.001-10% bymass.
 5. The nonaqueous electrolytic solution for nonaqueous-electrolytesecondary battery according to claim 1, which comprises the cyclicsulfonic acid ester in the nonaqueous electrolytic solution in an amountof 0.001-10% by mass.
 6. The nonaqueous electrolytic solution fornonaqueous-electrolyte secondary battery according to claim 1, whichcomprises the compound having a cyano group in the nonaqueouselectrolytic solution in an amount of 0.001-10% by mass.
 7. Thenonaqueous electrolytic solution for nonaqueous-electrolyte secondarybattery according to claim 1, which comprises the diisocyanate compoundin the nonaqueous electrolytic solution in an amount of 0.001-5% bymass.
 8. The nonaqueous electrolytic solution for nonaqueous-electrolytesecondary battery according to claim 1, wherein the concentration of theat least one salt selected from fluorophosphoric acid lithium salt otherthan LiPF₆ and lithium imide salt, and the lithium salt having an oxalicacid group in the nonaqueous electrolytic solution is 0.0005-0.5 mol/L.9. A nonaqueous-electrolyte secondary battery which comprises: anegative electrode and a positive electrode that are capable ofoccluding and releasing lithium ions; and the nonaqueous electrolyticsolution for nonaqueous-electrolyte secondary battery according toclaim
 1. 10. The nonaqueous-electrolyte secondary battery according toclaim 9, wherein the negative electrode comprises a current collectorand a negative-electrode active-material layer disposed on the currentcollector, the negative-electrode active-material layer containing anegative-electrode active material which comprises at least one memberselected from an elemental metal, alloys and compounds of silicon, andan elemental metal, alloys and compounds of tin.
 11. Thenonaqueous-electrolyte secondary battery according to claim 9, whereinthe negative electrode comprises a current collector and anegative-electrode active-material layer disposed on the currentcollector, the negative-electrode active-material layer containing anegative-electrode active material which comprises a carbonaceousmaterial.
 12. The nonaqueous-electrolyte secondary battery according toclaim 9, wherein the negative electrode comprises a current collectorand a negative-electrode active-material layer disposed on the currentcollector, the negative-electrode active-material layer containing anegative-electrode active material which comprises a lithium-titaniumcomposite oxide.
 13. The nonaqueous-electrolyte secondary batteryaccording to claim 9, wherein the positive electrode comprises a currentcollector and a positive-electrode active-material layer disposed on thecurrent collector, the positive-electrode active-material layercontaining one member selected from the group consisting oflithium-cobalt composite oxides, lithium-manganese composite oxides,lithium-cobalt-manganese composite oxides, lithium-nickel compositeoxides, lithium-cobalt-nickel composite oxides, lithium-nickel-manganesecomposite oxides, and lithium-nickel-cobalt-manganese composite oxides.14. The nonaqueous-electrolyte secondary battery according to claim 9,wherein the positive electrode comprises a current collector and apositive-electrode active-material layer disposed on the currentcollector, the positive-electrode active-material layer containingLi_(x)MPO₄ wherein M is one element selected from the group consistingof the Group-4 to Group-11 transition metals belonging to the fourthperiod of the periodic table, and x satisfies 0<x<1.2.
 15. Thenonaqueous electrolytic solution for nonaqueous-electrolyte secondarybattery according to claim 1, wherein the ratio of a molar content ofFSO₃ to a molar content of PF₆ in the nonaqueous electrolytic solutionis 0.01-0.5.
 16. The nonaqueous electrolytic solution fornonaqueous-electrolyte secondary battery according to claim 1, whereinthe ratio of the molar content of FSO₃ in the nonaqueous electrolyticsolution to the molar content of PF₆ in the nonaqueous electrolyticsolution is 0.001-0.5.